Photosensitive resin composition, photosensitive resin sheet, cured product, method for producing cured product, electronic component, and display device

Abstract

The present invention addresses the problem of providing a photosensitive resin composition that is highly sensitive and that is capable of pattern formation in which there is little pattern shrinkage during a curing reaction performed after exposure / development. Said problem is solved by a photosensitive resin composition containing: a resin including a repeating unit represented by formula (13); and a photosensitizer. (R1 and R2 each independently represents a hydrogen atom, a 1-6C alkyl group, or a 1-120C monovalent acid decomposable group. U represents a 1-120C tetravalent organic group; Y represents a 1-120C divalent organic group; and one or both among U and Y includes a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15).)

Description

Photosensitive resin composition, photosensitive resin sheet, cured product, method for producing cured product, electronic component, and display device

[0001] The present invention relates to a photosensitive resin composition suitable for use in electronic parts and display devices, and also to the photosensitive resin composition, a cured product, a photosensitive resin sheet, an electronic part, and a display device.

[0002] Polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance, electrical insulation, and mechanical properties, are widely used for surface protection films and interlayer insulating films used in electronic components, and for insulating layers and planarizing films used in display devices. In recent years, photosensitive resin compositions in which photosensitivity has been imparted to these resins themselves or their precursors, have been used (hereinafter, these photosensitive resin compositions will be referred to as "photosensitive resin compositions such as polyimide resins"). The use of photosensitive resin compositions such as polyimide resins can simplify the pattern processing step and shorten the complicated manufacturing process.

[0003] For photosensitive resin compositions such as polyimide resins, there have been proposed positive-type compositions in which the exposed areas are readily soluble in a developer and can be patterned, and negative-type compositions in which the composition itself is readily soluble and the exposed areas are insoluble in a developer. Generally, positive-type photosensitive resin compositions such as polyimide resins have superior resolution compared to negative-type compositions, and therefore are used in applications requiring fine processing.

[0004] Known positive photosensitive resin compositions such as polyimide resins include those obtained by adding a quinone diazide compound to a polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor (see, for example, Patent Document 1), and those obtained by adding a photoacid generator to a polyamide containing a protecting group that can be cleaved in the presence of an acid (see, for example, Patent Document 2).

[0005] However, the technology described in Patent Document 1 combines an alkali-soluble resin with a quinone diazide compound. The quinone diazide compound interacts with the alkali-soluble resin to reduce the solubility of the composition in an alkaline developer. On the other hand, the quinone diazide compound undergoes a photochemical reaction upon exposure to form an indene carboxylic acid compound, which acts as a dissolution promoter in an alkaline developer, resulting in a difference in dissolution rate between the unexposed and exposed areas, enabling pattern processing. In this technology, sensitivity depends on the amount of quinone diazide compound added, but increasing the amount of quinone diazide compound reduces the photochemical reaction rate due to the light absorption of the quinone diazide itself, limiting the improvement in sensitivity.

[0006] The technology disclosed in Patent Document 2 involves substituting the hydrogen atoms of hydroxyl groups in an alkali-soluble polyamide with protecting groups that can be removed in the presence of acid to produce an alkali-insoluble resin, which is then combined with a photoacid generator. This technology uses acid generated by the photoacid generator in exposed areas to remove the protecting groups from the polyamide, converting the polyamide from an alkali-insoluble to an alkali-soluble resin. This results in a difference in dissolution rate between exposed and unexposed areas, enabling positive-tone pattern processing. However, this technology has issues such as insufficient sensitivity improvement due to the low acid generation efficiency of the photoacid generator hindered by the light absorption of the polyamide, and the need to increase the protection rate to improve solubility in solvents.

[0007] JP 2011-180473 A JP 2011-221173 A

[0008] In recent years, due to the increasing size of substrates used and the need to improve productivity, it has become an issue to increase the sensitivity of the photosensitive resin compositions used.

[0009] SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition that has high sensitivity and excellent solvent solubility.

[0010] The main aspects of the photosensitive resin composition of the present invention are as follows: [1] A photosensitive resin composition containing (a) a resin ((a) resin) containing a repeating unit represented by formula (13), and (b) a photosensitizer.

[0011]

[0012] (R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms. U represents a tetravalent organic group having 1 to 120 carbon atoms, and Y represents a divalent organic group having 1 to 120 carbon atoms, and one or both of U and Y include a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15).

[0013]

[0014] (In formula (2), R ５ is the number of carbon atoms m １ is a cycloalkane-1,1-diyl group of the formula R ８ is a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) in the group, and when there are multiple groups, they may be the same or different. １ is an integer between 4 and 7, n １ is 1 to 2 m １ is an integer equal to or less than -2. ５ - (R ８ ) n １ is m １ If is even, then [m １ / 2+1] and the line connecting the carbon at the 1st position, m １ If is odd, then [(m １ +1) / 2] and the carbon at [(m １ The structure does not have line symmetry with respect to the line connecting the midpoint of the bond between the carbon atoms at positions [+1] / [2+1] and the carbon atom at position 1. * represents a bonding point. ６ and R ７ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group). ６ and R ７ do not have the same structure. * represents a bonding point. In formula (14) and formula (15), R ９each independently represent an alkyl group having 1 to 4 carbon atoms. * represents a bonding point.) [2] The photosensitive resin composition according to [1] above, wherein in formula (13), U is a tetravalent organic group having 1 to 120 carbon atoms containing a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15), and Y is a divalent organic group having 1 to 120 carbon atoms which may contain a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15). [3] The photosensitive resin composition according to [2] above, wherein all or part of the repeating units represented by formula (13) are repeating units represented by formula (1).

[0015]

[0016] (R １ and R ２ The explanation given in equation (13) is used. ３ and R ４ each independently represents an alkyl group having 1 to 4 carbon atoms, m ２ and n ２ each independently represents an integer of 0 to 3. X is a structure selected from the group consisting of formula (2) and formula (3), and V represents a divalent organic group having 1 to 120 carbon atoms which may contain a structure selected from the group consisting of formula (2) and formula (3). [4] The photosensitive resin composition according to item [3] above, wherein V in formula (1) is a divalent aromatic group having 6 to 50 carbon atoms, a linear or branched divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 9 carbon atoms, or a divalent group having an adamantane skeleton. [5] m in formula (1) ２ and n ２ is 0. [6] The photosensitive resin composition according to any one of [1] to [5] above, which does not contain a compound represented by formula (16), or, even if it contains one, the content thereof is 0.3 mass% or less when the total amount of the photosensitive resin composition is 100 mass%.

[0017]

[0018] (In formula (16), R １０ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R １１When a plurality of groups are present, each independently represents a monovalent organic group having 1 to 12 carbon atoms, s represents an integer of 2 or 3, and t represents an integer satisfying 0≦t≦(s+1). [7] The photosensitive resin composition according to any one of [1] to [6] above, wherein the (a) resin has a thermally crosslinkable group or a phenolic hydroxyl group at at least one molecular chain terminal. [8] The photosensitive resin composition according to any one of [1] to [7] above, wherein the (a) resin has a structure represented by formula (17) at at least one molecular chain terminal.

[0019]

[0020] (In formula (17), R １２ represents an organic group having 1 to 30 carbon atoms. * represents a bonding point.) [9] In the formula (17), R １２

[10] The photosensitive resin composition according to the above [8], wherein R ６ and R ７ The photosensitive resin composition according to any one of [1] to [9] above, which satisfies the following condition 1 or condition 2: Condition 1: R ６ and R ７ One of R is a hydrogen atom, and the other is a hydrocarbon group having 2 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) in the group. ６ and R ７ are hydrocarbon groups having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) within the group. ６ and R ７ are not the same structure.)

[11] In the formula (3), R ６ and R ７ The photosensitive resin composition according to the above

[10] , wherein R satisfies condition 2. ８ The total number of carbon atoms in the formula (3) is 1 or more and 5 or less, and ６ and R ７The photosensitive resin composition according to any one of [1] to

[11] above, wherein the total number of carbon atoms is 3 or more and 10 or less.

[13] The photosensitive resin composition according to any one of [1] to

[12] above, wherein the structure represented by formula (2) is any one of the structures represented by formulas (2-1) to (2-4).

[0021]

[0022] (In formula (2-1), R １３ ~R １８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １３ ~R １４ The total number of carbon atoms in R １７ ~R １８ The total number of carbon atoms in the formula (2-2) is not equal. １９ ~R ２８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ The total number of carbon atoms in the formula (2-3) is not equal. ２９ ~R ３６ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２９ ~R ３２ The total number of carbon atoms in R ３３ ~R ３６ The total number of carbon atoms in the formula (2-4) is not equal. ３７ ~R ４８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ３７ ~R ４２ The total number of carbon atoms in R ４３ ~R ４８ The total number of carbon atoms in the groups is not equal.)

[14] The photosensitive resin composition according to any one of the above [3] to

[13] , wherein X in the formula (1) is a group represented by any one of the formulas (5) to (12) and the formulas (18) to (24).

[0023]

[0024] (* represents a bonding point.)

[15] The photosensitive resin composition according to any one of [4] to

[14] above, wherein the divalent aromatic group having 6 to 50 carbon atoms represented by V in formula (1) is a group represented by either formula (25) or formula (26).

[0025]

[0026] (R ４９ ~R ５２ each independently represent a halogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. d and e each independently represent an integer from 0 to 4, f represents an integer from 1 to 3, and g and h each independently represent an integer from 0 to 3. Z represents a single bond, an ether group, a thioether group, a sulfone group, a ketone group, or a linear or branched alkylene group having 1 to 10 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. * represents a bonding point.)

[16] The photosensitive resin composition according to any one of [4] to

[15] above, wherein the divalent alicyclic group having 3 to 9 carbon atoms represented by V in formula (1) is a group represented by any one of formulas (27) to (29).

[0027]

[0028] (R ５３ ~R ５５ each independently represents a halogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. i represents an integer of 0 to 2, j represents an integer of 0 to 3, and k represents an integer of 0 to 3. * represents a bonding point. However, all R ５３ The total number of carbon atoms contained in R is 5 or less, and all R ５４ The total number of carbon atoms contained in R is 4 or less, and all R ５５ is 3 or less.)

[17] The photosensitive resin composition according to any one of [1] to

[16] above, further comprising a compound represented by formula (30) or a compound represented by formula (31), the content of which is 0.01 to 90 mass% when the total amount of the photosensitive resin composition is 100 mass%.

[0029]

[0030] (R ５６ each independently represents an alkyl group having 1 to 6 carbon atoms; R ５７ represents an alkyl group having 2 to 6 carbon atoms.)

[18] The photosensitive resin composition according to any one of [1] to

[17] above, wherein all or part of the (b) photosensitizer is a compound represented by formula (32):

[0031]

[0032] (R ５８ represents a trivalent to hexavalent alicyclic or aliphatic group having 1 to 20 carbon atoms; R ５９ When a plurality of Q's are present, each independently represents a monovalent aliphatic group having 1 to 6 carbon atoms. When a plurality of Q's are present, each independently represents a hydrogen atom, a 1,2-naphthoquinonediazide-4-sulfonyl group, or a 1,2-naphthoquinonediazide-5-sulfonyl group, provided that all of them cannot be hydrogen atoms. P1 represents an integer of 0 to 4, P2 represents an integer of 1 to 5, and P1 + P2 is an integer of 1 to 5. q represents an integer of 3 to 6.)

[19] The photosensitive resin composition according to any one of [1] to

[18] above, further comprising a compound having 3 to 6 aromatic rings in the molecule, each aromatic ring having one or more thermally crosslinkable groups bonded thereto.

[20] The (a) resin contains, as the repeating unit represented by formula (1), R １ and R ２ The photosensitive resin composition according to any one of [3] to

[19] above, wherein the photosensitive resin composition contains a repeating unit in which either or both of the repeating units are an alkyl group having 1 to 6 carbon atoms or a monovalent acid-decomposable group having 1 to 120 carbon atoms.

[21] The photosensitive resin composition according to any one of [1] to

[20] above, wherein, when the total mass of the resins contained in the photosensitive resin composition is taken as 100 mass%, the amount of fluorine atoms bonded to the molecular structure of the resin is less than 2 mass%.

[22] The photosensitive resin composition according to any one of [1] to

[21] above, further containing, as a resin other than the (a) resin, a resin containing at least one selected from the group consisting of a repeating unit represented by formula (33), a repeating unit represented by formula (34), and a repeating unit represented by formula (35).

[0033]

[0034] (Y１ each independently represents at least one tetravalent organic group selected from the group consisting of an aliphatic group having 2 to 20 carbon atoms, an alicyclic group having 4 to 40 carbon atoms, and an aromatic group having 6 to 40 carbon atoms. １ R each independently represents a divalent organic group having 2 to 40 carbon atoms. ６０ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having 2 to 20 carbon atoms and an ethylenically unsaturated double bond.)

[23] Z contained in the repeating unit represented by formula (33), the repeating unit represented by formula (34), and the repeating unit represented by formula (35) １ are each independently an organic group represented by any one of formulas (36) to (38).

[0035]

[0036] (X １ are each independently a direct bond or a divalent group represented by formula (39), and R ６１ each independently represents an alkyl group having 1 to 4 carbon atoms; X ２ is a divalent group represented by the formula (2) or a divalent group represented by the formula (3), each v independently represents 0 or 1, and * represents a bonding point to bond to the imide structure or amide structure.

[0037]

[0038] (* represents a bonding point on the imide bond or amide bond side. ** represents a bonding point on the benzene ring side.)

[24] A photosensitive resin sheet, in which the photosensitive resin composition according to any one of [1] to

[23] above is formed in the form of a film on a support.

[25] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[23] above.

[26] A method for producing a cured product, comprising the steps of: forming the photosensitive resin composition according to any one of [1] to

[23] above in the form of a film on a substrate; exposing the film of the photosensitive resin composition; developing the exposed film of the photosensitive resin composition; and curing the developed film of the photosensitive resin composition.

[27] An electronic component, comprising the cured product according to

[25] above.

[28] A display device, comprising the cured product according to

[25] above.

[0039] The photosensitive resin composition of the present invention has high sensitivity and excellent solvent solubility.

[0040] In this specification, the term "organic group" refers to a general term for an atomic group consisting of a hydrocarbon skeleton, and when used in a photosensitive resin composition, the hydrocarbon skeleton may contain a nitrogen atom (e.g., an amide bond), an oxygen atom (e.g., an ether bond, a ketone group, an ester bond), or a sulfur atom (e.g., a thioether bond, a thioketone group, a sulfonyl group, a thioester bond) in the hydrocarbon skeleton, provided that the organic group can be chemically identified with the hydrocarbon skeleton. Furthermore, the term "aromatic group" refers to a group that is part of an organic group and has an aromatic ring, the term "alicyclic group" refers to a group that is part of an organic group and has a cyclic structure that does not have aromaticity, and the term "aliphatic group" refers to a group that is part of an organic group and does not fall into either an aromatic group or an alicyclic group.

[0041] The photosensitive resin composition of the present invention contains (a) a resin containing a repeating unit represented by formula (13) (hereinafter simply referred to as "(a) resin"), and (b) a photosensitizer.

[0042]

[0043] (R １ and R ２each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms. U represents a tetravalent organic group having 1 to 120 carbon atoms, and Y represents a divalent organic group having 1 to 120 carbon atoms, and one or both of U and Y include a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15).

[0044]

[0045] (In formula (2), R ５ is the number of carbon atoms m １ is a cycloalkane-1,1-diyl group of the formula R ８ is a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) in the group, and when there are a plurality of such groups, they may be the same or different. １ is an integer between 4 and 7, n １ is 1 to 2 m １ is an integer equal to or less than -2. ５ - (R ８ ) n １ is m １ If is even, then [m １ / 2+1] and the line connecting the carbon at the 1st position, m １ If is odd, then [(m １ +1) / 2] and the carbon at [(m １ The structure does not have line symmetry with respect to the line connecting the midpoint of the bond between the carbon atoms at positions [+1] / [2+1] and the carbon atom at position 1. * represents a bonding point. ６ and R ７ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group). ６ and R ７ do not have the same structure. * represents a bonding point. In formula (14) and formula (15), R ９ each independently represents an alkyl group having 1 to 4 carbon atoms. * represents a bonding point.) <Resin Containing a Repeating Unit Represented by Formula (13) (Resin (a))> The photosensitive resin composition of the present invention contains resin (a).

[0046]

[0047] In formula (13), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms; U represents a tetravalent organic group having 1 to 120 carbon atoms; Y represents a divalent organic group having 1 to 120 carbon atoms; and one or both of U and Y include a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15).

[0048]

[0049] In formula (2), R ５ is the number of carbon atoms m １ is a cycloalkane-1,1-diyl group of the formula R ８ is a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) in the group, and when there are a plurality of such groups, they may be the same or different. １ is an integer between 4 and 7, n １ is 1 to 2 m １ is an integer equal to or less than -2. ５ - (R ８ ) n １ is m １ If is even, then [m １ / 2+1] and the line connecting the carbon at the 1st position, m １ If is odd, then [(m １ +1) / 2] and the carbon at [(m １ The structure does not have line symmetry with respect to the line connecting the midpoint of the bond between the carbon atoms at positions [+1 / 2+1] and the carbon atom at position 1. * indicates the bonding point.

[0050] In formula (3), R ６ and R ７ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group). ６ and R ７ do not have the same structure. * indicates a bond point.

[0051] In formula (14) and formula (15), R ９each independently represents an alkyl group having 1 to 4 carbon atoms. * represents a bonding point.

[0052] By introducing a structure with reduced symmetry represented by the formula (2), (3), or (14) or a bulky structure represented by the formula (15) into the main chain of the polymer, (a) interactions between resins and crystallization can be suppressed, and solubility in a solvent can be improved.

[0053] In the formula (2), R ５ is the number of carbon atoms m １ is a cycloalkane-1,1-diyl group of the formula m １ is an integer of 4 or more and 7 or less. (a) From the viewpoint of suppressing interactions between resins and crystallization and improving solubility in a solvent, m １ is preferably 5 or 6.

[0054] In the formula (2), R ８ represents a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) within the group. ８ When there are a plurality of these, they may be the same or different.

[0055] Specific examples of hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, ethylhexyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 2-propanoyl, 2-butyl, 2-methylbutanoyl, 3-methylbutyl, 2,2-dimethylpropyl, and ethenyl groups, of which methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, and ethylhexyl groups are preferred.

[0056] Specific examples of hydrocarbon groups containing an ether bond include a methoxymethyl group, a methoxyethyl group, a methoxybutyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxybutyl group, an ethoxypropyl group, and an ethoxybutyl group.

[0057] Specific examples of hydrocarbon groups containing a carbonyl group (ketone group) include ethanoyl, propanoyl, butanoyl, pentanoyl, acryloyl, and methacryloyl groups, with acryloyl and methacryloyl groups being preferred.

[0058] In the formula (2), n １ is 1 to 2 m １ In order to improve the solubility in a solvent, n is an integer of 0.01 to 0.2. １ is preferably an integer of 1 or more and 5 or less.

[0059] In the formula (2), R ５ - (R ８ ) n １ is m １ If is even, then [m １ The structure does not have line symmetry with respect to the line connecting the carbon at the [position] and the carbon at the 1 position. １ If is odd, then [(m １ +1) / 2] and the carbon at [(m １ The structure does not have a line symmetry with respect to the line connecting the midpoint of the bond between the carbon atoms at the positions [+1 / 2+1] and the carbon atom at the position 1. １ When is an even number, [m １ The line connecting the carbon atom at the [position] and the carbon atom at the 1st position is, for example, m １ When m = 6, it represents the dotted line (the dotted line passing through the 1st and 4th carbon atoms) in the structure shown in formula (44), and m １ When is odd, [(m １ +1) / 2] and the carbon at [(m １ The line connecting the midpoint of the bond between the carbon atoms at the positions [+1 / 2+1] and the carbon atom at the position 1 is, for example, １ = 5 represents the dotted line in the structure shown in formula (45) (the dotted line passing through the midpoints of the bonds between the 1-position carbon and the 3- and 4-position carbons).

[0060]

[0061] In formula (44) and formula (45), * represents a bonding point.

[0062] The absence of a line-symmetric structure in the formula (2) means that the structures on both sides of the dotted line in the formulas (44) and (45) do not overlap when rotated around the dotted line. ５ - (R ８ ) n １ The difference between stereoisomers (cis and anti configurations) when a quaternary carbon is included in the structure of m １ When ≡4, the formula (46) rotates around the dotted line and the structures overlap, resulting in a line-symmetric structure, whereas the formula (47) rotates around the dotted line and the structures do not overlap, resulting in a line-symmetric structure.

[0063]

[0064] In formulas (46) and (47), * represents a bonding point.

[0065] (a) In order to suppress interactions between resins and crystallization and improve solubility in a solvent, in the formula (2), R ８ The total number of carbon atoms in R is more preferably 1 or more and 5 or less, and even more preferably 2 or more and 5 or less. ８ The total number of carbon atoms in the cycloalkane-1,1-diyl group is 2 or more and 5 or less, and one of the carbon atoms in the cycloalkane-1,1-diyl group is R ８ It has a structure in which two are bonded together.

[0066]

[0067] * indicates the point of attachment.

[0068] Furthermore, (a) from the viewpoint of suppressing interactions between resins and crystallization and improving solubility in a solvent, it is preferable that the structure represented by formula (2) is any one of the structures represented by formulas (2-1) to (2-4).

[0069]

[0070] R １３ ~R 4８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0071] Preferred specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group.

[0072] In the formula (2-1), R １３ ~R １４ The total number of carbon atoms in R １７ ~R １８ The total number of carbon atoms in R １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ The total number of carbon atoms in R ２９ ~R ３２ The total number of carbon atoms in R ３３ ~R ３６ The total number of carbon atoms in R ３７ ~R ４２ The total number of carbon atoms in R ４３ ~R ４８ The total number of carbon atoms is not equal.

[0073] In addition, (a) from the viewpoint of heat resistance of the resin, in the formula (2-1), R １３ ~R １４ The total number of carbon atoms in R １７ ~R １８ In the formula (2-2), R １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ In the formula (2-3), R ２９ ~R ３２ The total number of carbon atoms in R ３３ ~R ３６ and in the formula (2-4), R ３７ ~R ４２ The total number of carbon atoms in R ４３ ~R ４８ The difference between the total carbon numbers of each of the groups is preferably 1 to 3.

[0074] In the formula (3), R ６ and R ７each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group). ６ and R ７ do not have the same structure. * indicates a bond point.

[0075] Specific examples of the hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group containing an ether bond, or the hydrocarbon group containing a carbonyl group (ketone group) include R ８ The same things as explained above can be mentioned.

[0076] (a) In order to suppress interactions between resins and crystallization and improve solubility in a solvent, in the formula (3), R ６ and R ７ It is desirable that the following condition 1 or 2 be satisfied.

[0077] Condition 1: R ６ and R ７ One of the groups is a hydrogen atom, and the other is a hydrocarbon group having 2 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) within the group.

[0078] Condition 2: R ６ and R ７ are hydrocarbon groups having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) within the group. ６ and R ７ are not identical in structure.) It is more preferable that the resin (a) used in the present invention satisfies condition 2.

[0079] In addition, in the formula (3), R ６ and R ７ It is more preferable that the total number of carbon atoms in R is 3 or more and 10 or less. ６ and R ７ The total number of carbon atoms in R is 4 or more and 8 or less, ６ and R ７ The difference in the number of carbon atoms between these is 2 or more.

[0080] Preferred specific examples of the groups represented by the formulas (2) to (3) include groups represented by the formulas (5) to (12) and (18) to (24), but are not limited thereto.

[0081]

[0082] In the formula (14) and the formula (15), R ９ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0083] Preferred examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. ９ is preferably a methyl group or an ethyl group.

[0084] In the formula (13), U represents a tetravalent organic group having 1 to 120 carbon atoms. １ ) (OR ２ ) is preferably a residue of a bisaminophenol compound or a residue of a compound in which the hydrogen atom of the phenolic hydroxyl group of a bisaminophenol compound is substituted with an organic group. When U is not a group containing a structure represented by the formula (2), formula (3), formula (14) or formula (15), U(OR １ ) (OR ２Specific preferred examples of the phenolic hydroxyl group include residues of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, bis(3-amino-4-hydroxyphenyl)sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2-bis(3-amino-4-hydroxyphenyl)propane, as well as residues in which the hydrogen atom of the phenolic hydroxyl group is substituted with an organic group.

[0085] In the formula (13), Y represents a residue of a dicarboxylic acid. When Y is not a group containing a structure represented by the formula (2), formula (3), formula (14), or formula (15), specific examples of groups that can be used as Y include residues corresponding to malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, biphenyldicarboxylic acid, 2,2-bis(carboxyphenyl)propane, 2,2-bis(carboxyphenyl)hexafluoropropane, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, diphenylmethanedicarboxylic acid, naphthalenedicarboxylic acid, adamantanedicarboxylic acid, and itaconic acid.

[0086] From the viewpoint of increasing sensitivity, it is preferable that U in formula (13) contains a structure represented by any one of formulas (2), (3), (14), and (15), and it is more preferable that all or a part of the repeating units represented by formula (13) are repeating units represented by formula (1).

[0087]

[0088] In the formula (1), R １ and R ２ is the same as that explained in the above formula (13), including the preferred range, and therefore the explanation is incorporated herein.

[0089] In the formula (1), R ３ and R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0090] Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-propyl group, a 2-butyl group, a tert-butyl group, and a 2-methylpropyl group. ３ and R ４ is preferably either a methyl group or an ethyl group.

[0091] In the formula (1), m ２ and n ２ each independently represents an integer of 0 to 3. (a) From the viewpoint of heat resistance of the resin, m ２ and n ２ is preferably 0.

[0092] In the formula (1), X is a structure selected from the group consisting of the formulas (2) and (3), and is directly bonded to the aromatic ring. From the viewpoint of improving solubility in a solvent, the preferred ranges of the formulas (2) and (3) are as described above, but it is more preferable that X in the formula (1) is a group represented by any one of the formulas (5) to (12) and the formulas (18) to (24), and even more preferable that X is a group represented by any one of the formulas (6), (7), (10), (12), (18), (19), (20), (21), (22), and (24).

[0093]

[0094] In the formula (1), V represents a divalent organic group having 1 to 120 carbon atoms which may contain a structure selected from the group consisting of formulas (2) and (3). From the viewpoint of reducing development residues, V in the formula (1) is preferably a divalent aromatic group having 6 to 50 carbon atoms, a linear or branched divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 9 carbon atoms, or a divalent group having an adamantane skeleton. Preferred specific examples include those given for Y in the description of the formula (13).

[0095] From the viewpoint of improving solubility in a solvent, V in the formula (1) is preferably a divalent aromatic group having 6 to 50 carbon atoms, a linear or branched divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 9 carbon atoms, or a divalent group having an adamantane skeleton.

[0096] Examples of the divalent aromatic group having 6 to 50 carbon atoms include a structure in which aromatic rings are linked by an organic group such as a single bond, an alkyl group, an ether group, a sulfide group, a sulfone group, or a ketone group. The number of carbon atoms in the divalent aromatic group having 6 to 50 carbon atoms is more preferably 6 to 30.

[0097] Specific examples of the divalent aromatic group having 6 to 30 carbon atoms include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenyl sulfone group, a diphenyl propane group, a diphenyl hexafluoropropane group, a diphenyl methane group, a diphenyl sulfide group, and a naphthalene group.

[0098] Examples of the linear or branched divalent aliphatic group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a butylene group, an isobutylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

[0099] The number of carbon atoms in the linear or branched divalent aliphatic group having 1 to 20 carbon atoms is more preferably 1 to 3. Examples of the linear or branched divalent aliphatic group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and an isopropylidene group.

[0100] Specific examples of the divalent alicyclic group having 3 to 9 carbon atoms include a cyclopropane group, a cyclobutane group, a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, a dimethylcyclohexane group, and a dimethylcyclobutane group.

[0101] V in the formula (1) preferably has two or more benzene rings. Examples of organic groups having two or more benzene rings include those in which benzene rings are bonded via organic groups, such as diphenyl ether, diphenyl sulfone, diphenyl ketone, and diphenylmethane, and those in which one or more sides of the benzene ring are shared, such as naphthalene and anthracene, forming a polycyclic aromatic group. Having two or more benzene rings reduces the concentration of amide groups in the polymer main chain, further reducing the intermolecular forces of the (a) resin, which has low symmetry and large steric hindrance, and improving its solubility in solvents. Furthermore, from the perspective of strengthening the interaction with the (b) photosensitizer and increasing sensitivity, it is more preferable that the divalent aromatic group having 6 to 50 carbon atoms represented by V in the formula (1) be a group of either formula (25) or formula (26).

[0102]

[0103] In the formula (25) and the formula (26), R ４９ ~R ５２ each independently represents a halogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. Preferred specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-propyl group, a 2-butyl group, a tert-butyl group, a 2-methylpropyl group, a trifluoromethyl group, and a pentafluoroethyl group.

[0104] In the formula (25) and the formula (26), d and e each independently represent an integer of 0 to 4, f represents an integer of 1 to 3, and g and h each independently represent an integer of 0 to 3. (a) From the viewpoint of the heat resistance of the resin, d and e are preferably 0, f is preferably 1, and g and h are preferably 0.

[0105] In the formula (25), Z represents a single bond, an ether group, a thioether group, a sulfone group, a ketone group, or a linear or branched alkylene group having 1 to 10 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. From the viewpoint of improving solubility in solvents, Z is preferably an ether group.

[0106] Furthermore, when V in the formula (1) has an alicyclic group having 4 to 6 carbon atoms, the polarity of the (a) resin, which has low symmetry and large steric hindrance, is further reduced, and the solubility in solvents is improved. Furthermore, from the viewpoint of improving the light transmittance of the (a) resin and improving its sensitivity, it is more preferable that V in the formula (1) be a group represented by any one of formulas (27) to (29).

[0107]

[0108] In the formulas (27) to (29), R ５３ ~R ５５ each independently represents a halogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. Preferred specific examples are a methyl group, an ethyl group, a propyl group, a butyl group, a 2-propyl group, a 2-butyl group, a tert-butyl group, a 2-methylpropyl group, a trifluoromethyl group, and a pentafluoroethyl group. In addition, i represents an integer of 0 to 2, j represents an integer of 0 to 3, and k represents an integer of 0 to 3. * represents a bonding point.

[0109] In the formulas (27) to (29), all of R ５３ The total number of carbon atoms contained in R is 5 or less, and all R ５４ The total number of carbon atoms contained in R is 4 or less, and all R ５５ The total number of carbon atoms contained in is 3 or less.

[0110] (a) From the viewpoint of the heat resistance of the resin, all R ５３ , all R ５４ and all R ５５ The total number of carbon atoms contained in is preferably 1 or less, and more preferably 0.

[0111] In the formula (13), R １ and R ２each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms. １ and -OR ２ is preferably bonded at the ortho position relative to an amide bond bonded to the same aromatic ring.

[0112] The acid-decomposable group referred to here is a group in which an acid generated from a photoacid generator by exposure to light is a group represented by —OR in the formula (13). １ and -OR ２ This refers to a functional group that can act on the photosensitive resin and convert it to -OH (phenolic hydroxyl group). The phenolic hydroxyl group increases the dissolution rate in an alkaline developer, so the difference in dissolution rate between the unexposed and exposed areas during development increases, allowing the exposed areas to dissolve, forming a relief pattern.

[0113] When an acid-decomposable group is used, -OR １ , -OR ２ The structure of can be converted into a phenolic hydroxyl group by the action of an acid. １ , -OR ２ The structure of the formula (I) is sometimes referred to as a "hydroxyl group protected by an acid-decomposable group." １ , -OR ２ The conversion of -OH to -OR by reaction with a protecting agent is called "deprotection." １ , -OR ２ The ratio converted into "protection rate" is called the "protection rate." The specific method for calculating the protection rate is as follows.

[0114] That is, the protection rate is 400 MHz, １ Measurement was performed using a H-NMR (nuclear magnetic resonance) spectrometer (AL-400 manufactured by JEOL Ltd.). Specifically, measurement was performed in a deuterated dimethyl sulfoxide solution with 16 cumulative measurements. When the integral value of the protons of the phenolic hydroxyl groups observed in the vicinity of 9 ppm to 11 ppm in the resin before protection is defined as M, and the integral value of the protons of the phenolic hydroxyl groups observed in the vicinity of 9 ppm to 11 ppm in the resin after protection is defined as N, the protection rate can be calculated using the following formula:

[0115] Protection rate (mol %)=(M−N) / M×100 By protecting a part of the phenolic hydroxyl groups in the polymer side chain, the solvent solubility is improved. Furthermore, (a) the solubility of the unexposed part of the resin in an alkaline developer is reduced, increasing the difference in dissolution rate with the exposed part, and from the viewpoint of increasing sensitivity, R in the formula (13) is １ and R ２ At least one of the groups is preferably an alkyl group having 1 to 6 carbon atoms or a monovalent acid-decomposable group having 1 to 120 carbon atoms, and more preferably a monovalent acid-decomposable group having 1 to 120 carbon atoms.

[0116] Specific examples of the monovalent acid-decomposable group having 1 to 120 carbon atoms include, but are not limited to, a t-butoxycarbonyl group, a t-butyl group, a tetrahydropyranyl group, and an (α-oxyalkyl)alkylene group.

[0117] From the viewpoint of improving the solubility of the photosensitive resin composition in a thinner (a low-boiling point solvent) used for edge-back rinsing of a substrate to which the photosensitive resin composition has been applied, the acid-decomposable group having 1 to 120 carbon atoms is preferably a t-butoxycarbonyl group or an (α-oxyalkyl)alkylene group, and more preferably an (α-oxyalkyl)alkylene group.

[0118] The (α-oxyalkyl)alkylene group includes the oxygen atom to which the group is bonded, and is defined as —O—CR ２ It is a group that forms an —O— bond (R is a hydrogen atom or an alkyl group). However, in the (α-oxyalkyl)alkylene group, the alkyl group and alkylene group in the (α-oxyalkyl)alkylene group may have a hydrogen atom in the alkyl group or alkylene group (excluding a hydrogen atom when the atom bonded to the α-position is a hydrogen atom) substituted with an oxyalkyl group, or may form a ring structure between two or more alkyl groups or between an alkyl group and an alkylene group. Specific examples of the structure include those shown in the formula below.

[0119]

[0120] In the above structure, R ６２ ~R ６７ , R ６９ represents a monovalent organic group, and R６８ and R ７０ indicates a divalent organic group. * indicates the bonding site with an oxygen atom.

[0121] Examples of the monovalent organic group include an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, and an alkoxycyclic alkyl group having 6 to 16 carbon atoms.

[0122] Examples of the divalent organic group include a propane-1,3-diyl group, a butane-1,3-diyl group, a pentane-1,3-diyl group, and a group in which a hydrogen atom of a group selected from the group consisting of a propane-1,3-diyl group, a butane-1,3-diyl group, and a pentane-1,3-diyl group has been substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxyalkyl group having 2 to 8 carbon atoms.

[0123] More preferred examples of the (α-oxyalkyl)alkylene group include groups represented by formula (40).

[0124]

[0125] In formula (40), R ７１ represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. ７２ and R ７３ represents an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. ７４ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. ７２ , R ７３ and R ７４ In two or all of the groups, the hydrogen atoms may be replaced with direct bonds to form a ring structure. * indicates the bonding site.

[0126] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups.

[0127] Specific examples of the alkoxyalkyl group having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, and a propoxybutyl group.

[0128] Specific examples of the cyclic alkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclopentylethyl group, a cyclohexylethyl group, a cycloheptylethyl group, a cyclopentylpropyl group, a cyclohexylpropyl group, and a cycloheptylpropyl group.

[0129] Specific examples of the alkoxy cyclic alkyl group having 6 to 16 carbon atoms include a methoxypentyl group, an ethoxypentyl group, a propoxypentyl group, a dimethoxypentyl group, a diethoxypentyl group, a dipropoxypentyl group, a trimethoxypentyl group, a triethoxypentyl group, a tripropoxypentyl group, a methoxyhexyl group, an ethoxyhexyl group, a propoxyhexyl group, a dimethoxyhexyl group, a diethoxyhexyl group, a dipropoxyhexyl group, a trimethoxyhexyl group, a triethoxyhexyl group, a tripropoxyhexyl group, a methoxyheptyl group, an ethoxyheptyl group, a propoxyheptyl group, a dimethoxyheptyl group, a diethoxyheptyl group, a dipropoxyheptyl group, a trimethoxyheptyl group, a triethoxyheptyl group, and a tripropoxyheptyl group.

[0130] Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexoxy group.

[0131] Formula (40) is the -OR of formula (13). １and -OR ２ R １ and R ２ is an (α-oxyalkyl) alkylene group, the carbon atom at the γ position, i.e., R ７２ Or R ７４ is a secondary carbon or a tertiary carbon. １ and R ２ is a group represented by formula (40), １ and -OR ２ This allows the activation energy for converting R to a phenolic hydroxyl group, i.e., for deprotection to be reduced. Therefore, even if only a small amount of acid is generated in the photosensitive composition upon exposure, deprotection can be achieved, and a highly sensitive photosensitive resin composition can be obtained. Specifically, R １ and R ２ is preferably a group represented by any one of formulas (41) to (43), and particularly preferably a group represented by formula (41).

[0132]

[0133] In formulas (41) to (43), * represents a bonding site with an oxygen atom.

[0134] The structure of a hydroxyl group protected by an acid-decomposable group can be obtained by reacting a resin having a hydroxyl group, including a phenolic hydroxyl group, with a protecting agent. For example, the resin having a hydroxyl group and the protecting agent are reacted in the presence of an acid or a base at a reaction temperature of −20 to 50° C. without a solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, or cyclopentanone, to obtain —OR １ and -OR ２ In this way, a resin (a) can be obtained in which the moiety is a hydroxyl group protected with an acid-decomposable group.

[0135] The protecting agent used in the present invention is a compound capable of protecting a hydroxyl group, and the protecting group introduced thereby can be deprotected by the action of an acid or a base. Any known protecting agent capable of protecting a hydroxyl group can be used as the protecting agent.

[0136] Examples of the protecting agent include R１ and R ２ is a 1-ethoxyethyl group, R １ and R ２ is a 2-tetrahydropyranyl group, R １ and R ２ When is to be a t-butoxycarbonyl group, di-tert-butyl dicarbonate can be used.

[0137] An acid or base catalyst can be used in the reaction of a resin having a hydroxyl group, including a phenolic hydroxyl group, with a protecting agent to obtain a resin having a hydroxyl group structure protected by an acid-decomposable group.

[0138] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. Organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.

[0139] Examples of the base catalyst include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine.

[0140] The (a) resin used in the present invention can be synthesized by known methods. For example, it can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, the corresponding dicarboxylic acid chloride, or a dicarboxylic acid activated ester. In the (a) resin, the repeating unit represented by formula (13) accounts for 40 mol% or more, preferably 60 mol% or more, and particularly preferably 80 mol% or more of all repeating units, with the upper limit being 100 mol%. Furthermore, the (a) resin may contain other repeating units having an α-hydroxy(alkyl or hydrogen)arylamide structure in addition to the repeating units represented by formula (13). The repeating units having an α-hydroxy(alkyl or hydrogen)arylamide structure are obtained by reacting a bisaminophenol with a dicarboxylic acid, a dicarboxylic acid chloride, or a dicarboxylic acid activated ester. Furthermore, the (a) resin may contain copolymerizable repeating units other than the α-hydroxy(alkyl or hydrogen)arylamide structure in an amount of less than 30 mol%, preferably 20 mol% or less, and more preferably 10 mol% or less of all repeating units.

[0141] The main chain terminals of the resin (a) used in the present invention may be capped with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monocarboxylic acid chloride compound, a monoactive ester compound, etc. Capping the main chain terminals with a terminal capping agent can improve the storage stability of the photosensitive resin composition.

[0142] The introduction ratio of the monoamine used as the end-capping agent is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 80 mol% or more, based on 100 mol% of the terminal carboxyl groups contained in the (a) resin before capping. Furthermore, the introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the end-capping agent is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 80 mol% or more, based on 100 mol% of the terminal amino groups contained in the (a) resin before capping. Multiple end-capping agents may be used.

[0143] (a) The capping rate of the main chain end of the resin is 400 MHz, １ Measurement was performed using a H-NMR (nuclear magnetic resonance) spectrometer (AL-400 manufactured by JEOL Ltd.). Specifically, measurement was performed 16 times in a deuterated dimethyl sulfoxide solution. When the theoretical integral of protons attributable to functional groups specific to the terminal structure (e.g., thermally crosslinkable groups) when 100% of the main chain terminals are reacted with the terminal capping agent is defined as H1, and the integral of protons attributable to the same functional groups actually observed above is defined as H2, the capping rate of the main chain terminals can be calculated using the following formula:

[0144] Capping rate of main chain ends (mol %)=H2 / H1×100.

[0145] Specific examples of monoamines used as end-capping agents include propylamine, isopropylamine, butylamine, aniline, o-aminophenol, m-aminophenol, p-aminophenol, and 4-aminostyrene.

[0146] Specific examples of acid anhydrides used as end-capping agents include nadic anhydride, maleic anhydride, acrylic anhydride, methacrylic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

[0147] Specific examples of the monocarboxylic acid chloride compound include acryloyl chloride, methacryloyl chloride, butyryl chloride, propionic acid chloride, 2-ethylhexanoic acid chloride, cyclohexanecarboxylic acid chloride, benzoyl chloride, naphthoyl chloride, heptanoic acid chloride, isobutyryl chloride, isononanoyl chloride, neodecanoyl chloride, octanoyl chloride, pivaloyl chloride, valeroyl chloride, methoxyacetyl chloride, acetoxyacetyl chloride, phenylacetyl chloride, cinnamoyl chloride, and acetyl chloride.

[0148] A specific example of the mono-active ester compound is N-benzoylimidazole.

[0149] From the viewpoint of minimizing shrinkage of the film during curing, it is preferable that at least one of the terminal structures of the resin (a) has a thermally crosslinkable group or a phenolic hydroxyl group. Specific examples of the thermally crosslinkable group include a methylol group, an alkoxymethyl group, a vinyl group, an ethynyl group, an epoxy group, a glycidyl group, an oxetanyl group, and a maleimide group.

[0150] Similarly, from the viewpoint of minimizing shrinkage of the film during curing, it is preferable that the (a) resin has a structure represented by formula (17) at least at one of the molecular chain terminals.

[0151]

[0152] In the formula (17), R １２ represents an organic group having 1 to 30 carbon atoms. Specific examples of the organic group having 1 to 30 carbon atoms include the same as those of the residue of the monocarboxylic acid chloride compound.

[0153] Among these, in the formula (17), R １２It is more preferable that the (a) resin has a thermally crosslinkable group. Specific examples of the thermally crosslinkable group include a methylol group, an alkoxymethyl group, a vinyl group, an ethynyl group, an epoxy group, a glycidyl group, an oxetanyl group, and a maleimide group. The weight-average molecular weight of the (a) resin, measured by gel permeation chromatography, is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 60,000, in terms of polystyrene. By setting the weight-average molecular weight of the (a) resin within the above range, it is possible to easily achieve good solvent solubility, good solubility in a developer, and high mechanical strength.

[0154] The weight-average molecular weight was measured using a gel permeation chromatography (GPC) analyzer under the following conditions: Measuring device: Waters 2695 (manufactured by Waters Corporation) Column temperature: 50°C Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21% by mass of lithium chloride and 0.48% by mass of phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).

[0155] <(b) Photosensitizer> The (b) photosensitizer used in the present invention is a compound that has the function of generating an acid upon exposure to light or a compound that itself is transformed into an acidic compound upon exposure to light. Any known (b) photosensitizer can be used as long as it does not impair the effects of the present invention.

[0156] Specific examples of (b) photosensitizers include ester compounds of polyhydric phenol compounds and naphthoquinone diazide sulfonic acid compounds, onium salt-type ionic photoacid generators, and nonionic photoacid generators. An onium salt is a compound formed when a compound having an electron pair not involved in a chemical bond forms a coordinate bond with another cationic compound via that electron pair. The ionic photoacid generators are characterized in that the cationic moiety of the onium salt determines the photochemical properties (molar absorption coefficient, absorption wavelength, and quantum yield), while the anionic moiety determines the strength of the acid generated. On the other hand, nonionic photoacid generators are photoacid generators in which the light-absorbing moiety and the acid are connected via an ester bond.

[0157] Examples of polyhydric phenol compounds used in the ester compound of a polyhydric phenol compound and a naphthoquinone diazide sulfonic acid compound include Bis-Z, TekP-4HBPA, TekOC-4HBPA, TrisP-HAP, TrisP-PA, BisP-AP, BisP-3MZ, Bis25X-F, BisOC-FL, BisP-MIBK, DML-PC, DML-POP, TML-BPA, and TMOM-BP (trade names, all of which are sold in Honshu, Japan). Examples of suitable compounds include bisphenol A, bisphenol E, methylene bisphenol A, bisphenol E, and the like.

[0158] It is preferable to contain an ester compound of a polyhydric phenol compound represented by formula (32) and a naphthoquinone diazide sulfonic acid compound as the (b) photosensitizer, from the viewpoint that the interaction with the (a) resin, which has low symmetry and large steric hindrance, is strengthened, the solubility of the unexposed parts of the (a) resin in an alkaline developer is reduced, and the difference in dissolution rate with the exposed parts is increased, resulting in improved pattern dimensional accuracy after development.

[0159]

[0160] In the formula (32), R ５８represents a trivalent to hexavalent alicyclic or aliphatic group having 1 to 20 carbon atoms. Specific preferred examples of the alicyclic or aliphatic group having 1 to 20 carbon atoms include the structures shown below. In the structures below, * represents a bonding point, and the number of bonding points corresponds to q.

[0161]

[0162] In the formula (32), R ５９ each independently represents a monovalent aliphatic group having 1 to 6 carbon atoms. Preferred specific examples of the monovalent aliphatic group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-propanoyl group, a 2-butyl group, a 2-methylbutanoyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, and an ethenyl group. Of these, it is preferable to use a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, or a hexyl group.

[0163] In the formula (32), each Q independently represents a hydrogen atom, a 1,2-naphthoquinonediazide-4-sulfonyl group, or a 1,2-naphthoquinonediazide-5-sulfonyl group, provided that all Qs are not hydrogen atoms.

[0164] In the formula (32), P1 represents an integer of 0 to 4. P2 represents an integer of 1 to 5, and P1+P2 is an integer of 1 to 5. From the viewpoint of the heat resistance of the resin composition, P1 is preferably 0 or 1, and P2 is preferably 1 or 2.

[0165] In the formula (32), q represents an integer of 3 to 6. From the viewpoint of the heat resistance of the resin composition, q is preferably 3 or 4.

[0166] Preferred specific examples of the formula (32) include the following structures: wherein Q is as explained above.

[0167]

[0168] The esterification rate of the formula (32), i.e., the proportion of Q's that are 1,2-naphthoquinonediazide-4-sulfonyl groups or 1,2-naphthoquinonediazide-5-sulfonyl groups, is preferably 50 mol % or more, and more preferably 75 mol % or more, when the total amount of Q is taken as 100 mol %. When the ratio is in this range, the difference in dissolution rate between the unexposed and exposed areas is increased, resulting in improved pattern dimensional accuracy after development.

[0169] The content of the compound represented by the formula (32) is 1% by mass or more, preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, relative to 100% by mass of the (a) resin.

[0170] In particular, the resin (a) is represented by the formula (2), R ８ The total number of carbon atoms in R is 2 or more and 5 or less, and ５ R is attached to one of the carbon atoms of the cycloalkane-1,1-diyl group represented by ８ a resin containing a structure in which two of R are bonded, more specifically, a resin containing any of the structures represented by the formula (6), the formula (7), the formula (22) and the formula (24), or a resin containing any of the structures represented by the formula (3), R ６ and R ７ are hydrocarbon groups each having 1 to 10 carbon atoms, and R ６ and R ７ are not identical structures, and all R ６ and R ７ The total number of carbon atoms in R is 4 or more and 8 or less, ６ and R ７ In the case of a resin having a significantly reduced symmetry, such as a resin containing a structure in which the difference in the number of carbon atoms between the groups represented by the formulas (10), (12), (18), (19) and (20) is 2 or more, the pattern dimensional accuracy after development can be further improved.

[0171] The ionic photoacid generator is preferably one that does not contain heavy metals or halogen ions, and more preferably a triorganosulfonium salt compound. Specific examples of the triorganosulfonium salt compound include triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate ("SP-056", product name, manufactured by ADEKA Corporation); the sulfonates of dimethyl-1-naphthylsulfonium; the sulfonates of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the sulfonates of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the sulfonates of diphenyliodonium.

[0172] As the nonionic photoacid generator, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, an oxime sulfonate compound, an imide sulfonate compound, or the like can be used.

[0173] A specific example of the diazomethane compound is bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0174] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred examples of the sulfone compound include 2-(p-toluenesulfonyl)acetophenone and bis(phenylsulfonyl)methane.

[0175] Specific examples of the sulfonate ester compound include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, iminosulfonate ester compounds, etc. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenyl sulfonate.

[0176] Specific examples of carboxylic acid ester compounds include carboxylic acid 2-nitrobenzyl esters.

[0177] Specific examples of the oxime sulfonate compound include "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (benzeneacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (benzeneacetonitrile, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylidene), and PAG-203 (all manufactured by BASF Japan Ltd.), and PAI-101 ((Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Co., Ltd.).

[0178] Specific examples of the imide sulfonate compound include N-hydroxynaphthalimide triflate, "ADEKA ARCLES" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalimide triflate, manufactured by ADEKA Corporation), NA-101 (N-hydroxynaphthalimide-p-toluenesulfonate), and NA-106 (N-hydroxynaphthalimide camphorsulfonate, all manufactured by Midori Chemical Industry Co., Ltd.).

[0179] In the photosensitive resin composition of the present invention, the content of the (b) photosensitizer is preferably 1 to 100 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of the (a) resin, in terms of the difference in dissolution rate between the exposed portion and the unexposed portion and the tolerance range of sensitivity.

[0180] The photosensitive resin composition of the present invention may contain components other than (a) the resin and (b) the photosensitizer, to the extent that the object of the present invention is not impaired or for the purpose of imparting additional functions. Such components include known components such as resins other than (a) the resin or precursors thereof, solvents, amine compounds, dissolution accelerators, sensitizers, silane coupling agents, surfactants, etc.

[0181] <Resin Other Than (a) Resin or Precursor Thereof> From the viewpoint of increasing sensitivity, the photosensitive resin composition of the present invention may further contain, as a resin other than (a) resin, a resin containing at least one repeating unit selected from the group consisting of a repeating unit represented by formula (33), a repeating unit represented by formula (34), and a repeating unit represented by formula (35). In other words, these resins have an imide ring or are intended to form an imide ring.

[0182]

[0183] In the formula (33), the formula (34) and the formula (35), Y １ each independently represents at least one tetravalent organic group selected from the group consisting of an aliphatic group having 2 to 20 carbon atoms, an alicyclic group having 4 to 40 carbon atoms, and an aromatic group having 6 to 40 carbon atoms.

[0184] Preferred Y １ Preferred specific examples of include, but are not limited to, the residues of the following acid dianhydrides.

[0185] (Preferred specific examples of acid dianhydrides) diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, bifevir tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(isopropylidene)diphthalic anhydride, diphenylmethane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione.

[0186] In the formula (33), the formula (34) and the formula (35), Z １ each independently represents a divalent organic group having 2 to 40 carbon atoms. １Preferred examples of the above include, but are not limited to, residues of diamines having hydroxyl groups and structures in which the hydroxyl groups of these residues are partially or completely protected.

[0187] Examples of such diamines having a hydroxyl group include 2,4-diaminophenol, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and bis(3-amino-4-hydroxyphenyl)sulfone.

[0188] Furthermore, the compound may contain residues of the following diamines to the extent that pattern processability is not impaired.

[0189] (Specific examples of diamines that provide the diamine residue) paraphenylenediamine, metaphenylenediamine, toluylenediamine, benzidine, orthotolidine, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ketone, diaminodiphenyl sulfide, bis(aminophenyl)propane, bis(aminophenyl)hexafluoropropane, bis(trifluoromethyl)benzidine, and water additives thereof, butanediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

[0190] From the viewpoint of increasing sensitivity, Z １ are each independently an organic group represented by any one of formulas (36) to (38), where * represents a bonding point to the imide structure or amide structure.

[0191]

[0192] In the formulas (36), (37) and (38), X １ are each independently a direct bond or a divalent group represented by formula (39). １is preferably a direct bond.

[0193] In the formulas (36), (37) and (38), R ６１ each independently represents an alkyl group having 1 to 4 carbon atoms. Preferred specific examples are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a t-butyl group.

[0194] In the formula (36), X ２ is a divalent organic group represented by the formula (2) or (3). The preferred ranges of formula (2) and formula (3) are the same as those explained for formula (13), and therefore, are incorporated herein by reference.

[0195] In the formula (36), each v independently represents 0 or 1. (a) From the viewpoint of the heat resistance of the resin, v is preferably 0.

[0196]

[0197] In the formula (39), * represents a bonding point to the imide structure or amide structure, and ** represents a bonding point to the aromatic ring.

[0198] In the formula (33) and the formula (35), R ６０ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having 2 to 20 carbon atoms and an ethylenically unsaturated double bond. ６０ Specific examples of the group include a methyl group, an ethyl group, a 2-methacryloyloxyethyl group, and a 2-acryloyloxyethyl group.

[0199] <Thermal Crosslinking Agent> From the viewpoint of reducing the shrinkage of the film during curing, the resin composition of the present invention preferably contains a thermal crosslinking compound having, in the molecule, 3 to 6 aromatic rings to which one or more thermal crosslinking groups are bonded.

[0200] In particular, the resin (a) is represented by the formula (2), R ８ The total number of carbon atoms in R is 2 or more and 5 or less, and ５ R is attached to one of the carbon atoms of the cycloalkane-1,1-diyl group represented by ８More specifically, resins containing structures represented by the formula (6), formula (7), formula (22) and formula (24), and resins containing structures represented by the formula (3), R ６ and R ７ are hydrocarbon groups each having 1 to 10 carbon atoms, and R ６ and R ７ are not identical structures, and all R ６ and R ７ The total number of carbon atoms in R is 4 or more and 8 or less, ６ and R ７ When blended with a resin having a significantly reduced symmetry, such as a resin containing a structure in which the difference in the number of carbon atoms between the groups is 2 or more, more specifically, a resin containing a structure represented by the above formula (10), formula (12), formula (18), formula (19) and formula (20), it becomes possible to further reduce the shrinkage of the film upon curing.

[0201] Specific examples of the thermal crosslinkable group include a methylol group, an alkoxymethyl group, a vinyl group, an ethynyl group, an epoxy group, a glycidyl group, and an oxetanyl group. Of these, the thermal crosslinking agent preferably has a methylol group or an alkoxymethyl group, more preferably an alkoxymethyl group.

[0202] Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

[0203] Preferred examples of such compounds include HMOM-TPPHBA and HMOM-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), VG3101L (trade name, manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark) S, "TEPIC" G, and "TEPIC" P (trade names, manufactured by Nissan Chemical Industries, Ltd.), "Epiclon" N660, "Epiclon" N695, and HP7200 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), "Denacol" EX-321L (trade name, manufactured by Nagase ChemteX Corporation), NC6000, and EPPN502H. , NC3000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EHPE-3150 (trade name, manufactured by Daicel Corporation), compounds having an oxetanyl group include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all trade names, manufactured by Toagosei Co., Ltd.), "Etanacol" (registered trademark) OXBP, "Etanacol" OXTP (all trade names, manufactured by Ube Industries, Ltd.), and can be obtained from each of the above companies.

[0204] In the photosensitive resin composition of the present invention, the content of the thermal crosslinking agent is preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the (a) resin. By making the content of the thermal crosslinking agent 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the (a) resin, pattern shrinkage during curing is reduced. Furthermore, by making the content of the thermal crosslinking agent 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the (a) resin, a decrease in elongation of the cured product can be prevented.

[0205] <Compound Represented by Formula (16)> From the viewpoint of being able to reduce the change in sensitivity depending on the time from exposure to development, the photosensitive resin composition of the present invention preferably does not substantially contain a compound represented by formula (16), and even if it does contain one, the content thereof is preferably 0.3% by mass or less when the total amount of the photosensitive resin composition is taken as 100% by mass. Here, the meaning of "substantially" means that it is below the detection limit in the measurement method described in the Examples section.

[0206]

[0207] In formula (16), R １０ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. From the viewpoint of film shrinkage during curing, R １０ The effect is more pronounced when the group is a methyl group or an ethyl group, and more pronounced when the group is a methyl group.

[0208] In formula (16), R １１ When a plurality of R are present, each independently represents a monovalent organic group having 1 to 12 carbon atoms. １１ When the group is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, the effect on the sensitivity change is large, the effect is more pronounced when the group is a methyl group or an ethyl group, and the effect is even more pronounced when the group is a methyl group.

[0209] In formula (16), s is 2 or 3. (a) When considering the effect on compatibility with resins and on film shrinkage during curing, when s is 2, the effect is greater.

[0210] In formula (16), t represents an integer that satisfies 0≦t≦(s+1). From the viewpoint of suppressing shrinkage of the film during curing, t is preferably 0.

[0211] Examples of the compound represented by formula (16) include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, and 1,5-dimethyl-2-piperidone.

[0212] From the viewpoint of being able to reduce a change in sensitivity due to the elapsed time from exposure to development, the content of the compound represented by formula (16) contained in the photosensitive resin composition is preferably 0.02% by mass or less, more preferably 0.005% by mass or less, and even more preferably 0% by mass, when the total amount of the photosensitive resin composition is 100% by mass.

[0213] The present inventors have found that the compound represented by formula (16), which is sometimes used as a general-purpose solvent in polymer polymerization and the like, when coexists with a resin (a) that has low symmetry and high steric hindrance, the change in sensitivity with respect to the time from exposure to development becomes larger than that in the case of a resin with high symmetry.

[0214] From this viewpoint, it is preferable not to use the compound represented by formula (16) when synthesizing the polymer or preparing the photosensitive resin composition.

[0215] In particular, the resin (a) is represented by the formula (2), R ８ The total number of carbon atoms in R is 2 or more and 5 or less, and ５ R is attached to one of the carbon atoms of the cycloalkane-1,1-diyl group represented by ８ More specifically, resins containing structures represented by the formula (6), formula (7), formula (22) and formula (24), and resins containing structures represented by the formula (3), R ６ and R ７ are hydrocarbon groups each having 1 to 10 carbon atoms, and R ６ and R ７ are not identical structures, and all R ６ and R ７ The total number of carbon atoms in R is 4 or more and 8 or less, ６ and R ７ In resins with a significantly reduced symmetry, such as resins containing a structure in which the difference in the number of carbon atoms between the groups represented by the formulas (10), (12), (18), (19) and (20) is 2 or more, it is possible to further reduce the change in sensitivity due to the elapsed time from exposure to development.

[0216] <Compound Represented by Either Formula (30) or Formula (31)> From the viewpoint of reducing a change in sensitivity after storage of the composition at room temperature, the photosensitive resin composition of the present invention preferably contains the compound represented by either Formula (30) or Formula (31) in a total amount of 0.01 to 90 mass % when the total amount of the photosensitive resin composition is taken as 100 mass %.

[0217]

[0218] In the formula (30) and the formula (31), R ５６ each independently represents an alkyl group having 1 to 6 carbon atoms. Preferred specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-propanoyl group, a 2-butyl group, a 2-methylbutanoyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, and an ethenyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, or a hexyl group is preferred.

[0219] In the above (31), R ５７ represents an alkyl group having 2 to 6 carbon atoms. Preferred specific examples of the alkyl group having 2 to 6 carbon atoms include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-propanoyl group, a 2-butyl group, a 2-methylbutanoyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, and an ethenyl group, and preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, or a hexyl group.

[0220] From the viewpoint of reducing a change in sensitivity after storage of the composition at room temperature, the total content of the compounds represented by either Formula (30) or Formula (31) is preferably 0.01 to 10 mass%, more preferably 0.01 to 5 mass%, and even more preferably 0.01 to 1 mass%, when the total amount of the photosensitive resin composition is taken as 100 mass%.

[0221] In particular, the resin (a) is represented by the formula (2), R ８ The total number of carbon atoms in R is 2 or more and 5 or less, ８ In particular, resins containing structures represented by the formula (6), the formula (7), the formula (22) and the formula (24), and resins containing structures represented by the formula (3), ６ and R ７are hydrocarbon groups each having 1 to 10 carbon atoms, and R ６ and R ７ are not identical structures, and all R ６ and R ７ The total number of carbon atoms in R is 4 or more and 8 or less, ６ and R ７ When blended with a resin having a significantly reduced symmetry, such as a resin having a structure in which the difference in the number of carbon atoms between the groups is 2 or more, more specifically, a resin having a structure represented by the above formula (10), formula (12), formula (18), formula (19) and formula (20), it becomes possible to further reduce the change in sensitivity after storage of the composition at room temperature.

[0222] <Solvent> The positive photosensitive resin composition of the present invention preferably further contains a solvent (hereinafter, may be referred to as "(c) solvent"). By containing a solvent, the coating property is improved, and a homogeneous positive photosensitive resin film can be obtained. Any known (c) solvent can be used as long as it does not impair the effects of the present invention. Note that the compound represented by either formula (30) or formula (31) or the compound represented by formula (16) may also function as a solvent.

[0223] The (c) solvent is not particularly limited as long as it can dissolve or disperse the (a) resin and (b) photosensitizer, but suitable solvents include amide-based solvents, ester-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, and dimethyl sulfoxide.

[0224] Specific examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropyleneurea.

[0225] Specific examples of the ester solvent include γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate.

[0226] Specific examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, and propylene glycol.

[0227] Specific examples of ether solvents include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether.

[0228] Specific examples of ketone solvents include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.

[0229] As the (c) solvent, it is preferable to use an aprotic solvent having a relative dielectric constant in the range of 5 to 20, and the relative dielectric constant of the (c) solvent is more preferably 6 to 19, and even more preferably 7 to 19.

[0230] (c) By using an aprotic solvent having a relative dielectric constant in the range of 5 to 20 as the solvent, the stability of the photosensitive resin composition as a solution during storage is improved.

[0231] Examples of aprotic solvents having a dielectric constant in the range of 5 to 20 include tetrahydrofuran (dielectric constant 7.6), propylene glycol monomethyl ether acetate (dielectric constant 8.3), methyl isobutyl ketone (dielectric constant 13.1), cyclopentanone (dielectric constant 14.5), cyclohexanone (dielectric constant 18.3), and methyl ethyl ketone (dielectric constant 18.5).

[0232] The (c) solvent is preferably an aprotic solvent having 3 to 12 carbon atoms, and the number of carbon atoms of such an aprotic solvent is more preferably 4 to 10. An aprotic solvent having 3 to 12 carbon atoms has excellent solubility for the (a) resin used in the photosensitive resin composition of the present invention. Therefore, by using an aprotic solvent having 3 to 12 carbon atoms in the photosensitive resin composition of the present invention, the solids concentration of the photosensitive resin composition can be increased, and by applying a composition containing such a solvent, it becomes easy to obtain a film of the photosensitive resin composition with a large thickness, for example, a thickness of 1 μm or more.

[0233] In the present invention, the content of the (c) solvent is preferably 100 parts by mass or more relative to 100 parts by mass of the (a) resin in order to enhance the stability of the solution, and on the other hand, it is preferably 1,500 parts by mass or less in order to form a thick film of the photosensitive resin composition, specifically a film with a thickness of 1 μm or more.

[0234] <Amine Compound> The photosensitive resin composition of the present invention preferably further contains an amine compound having a molecular weight of 1,000 or less (hereinafter, may be referred to as "(d) amine compound"). By containing the (d) amine compound, deprotection is suppressed during pre-baking, which will be described later. Therefore, a pattern of the photosensitive resin composition can be obtained with little reduction in the developed film.

[0235] As the (d) amine compound, it is preferable to use an amine compound whose conjugate acid has a pKa in the range of 4.5 to 10.8, more preferably an amine compound whose pKa is 5.0 to 10.0, and even more preferably an amine compound whose pKa is 6.0 to 9.0. When the pKa of the conjugate acid of the (d) amine compound is in the above range, deprotection during pre-baking is suppressed and acid generated during exposure is less likely to be neutralized, making it possible to obtain a photosensitive resin composition pattern with little film loss upon development.

[0236] Examples of amine compounds having a conjugate acid with a pKa in the above range include aniline (pKa=4.6), dimethylaniline (pKa=5.20), pyridine (pKa=5.25), 2-picoline (pKa=5.97), 2,6-lutidine (pKa=6.75), imidazole (pKa=6.95), N-methylmorpholine (pKa=7.38), morpholine (pKa=8.36), dicyclohexylamine (pKa=10.4), and cyclohexylamine (pKa=10.6).

[0237] In the present invention, the content of the (d) amine compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the (a) resin. When the content of the (d) amine compound is within the above range, a highly sensitive photosensitive resin composition pattern with little film loss can be obtained.

[0238] <Fluorine Atom Content> In the photosensitive resin composition of the present invention, when the total mass of all resins contained in the photosensitive resin composition is taken as 100 mass%, the content of fluorine atoms contained in the structure of all resins is preferably less than 2 mass%. When the content of fluorine atoms contained in the structure of all resins is less than 2 mass%, the hydrophobicity of the photosensitive resin composition is reduced. This increases affinity with the developer and suppresses the generation of residues, thereby achieving high sensitivity. Here, the meaning of fluorine atoms includes those present as ions.

[0239] The content of fluorine atoms contained in all resins when the total amount of all resins contained in the photosensitive resin composition is taken as 100 mass % can be analyzed by the following method.

[0240] First, the resin is separated from the photosensitive resin composition. The separated resin is precisely weighed as a sample. Using an automatic sample combustion device, the resin is burned in the combustion tube of an analyzer, and the generated gas is absorbed into a solution. A portion of the absorbed solution is then analyzed by ion chromatography. 0.036% by mass of hydrogen peroxide water can be used as the absorbed solution. The specific measurement method is as follows.

[0241] The resin was separated from the photosensitive resin composition using high-performance liquid chromatography, and the separated resin was precisely weighed as a sample. Using the automatic sample combustion apparatus described below, the resin was combusted in a combustion tube of an analyzer. The generated gas was absorbed in the following absorption liquid, and a portion of the absorption liquid was analyzed by ion chromatography. The resin mass was taken as 100% by mass, and the mass of fluorine atoms relative to this was calculated as a percentage (mass%).

[0242] <Resin separation conditions> System: LC-10Avp series manufactured by Shimadzu Corporation Detector: Photodiode array detector (UV=254 nm) Flow rate: 1 mL / min Column temperature: 50°C Mobile phase: NMP (containing 0.21% by mass of lithium chloride and 0.48% by mass of phosphoric acid) The column to be used is selected based on the properties of the resin and is capable of performing separation.

[0243] <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C Outlet 1000°C Gas: Ar / O ２ 200mL / min :O ２ / 400 mL / min Absorption liquid: H ２ O ２ 0.036 mass%, internal standard P 4 μg / mL Amount of absorption solution: 20 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DINONEX Co., Ltd.) Mobile phase: 2.7 mmol / L Na ２ CO ３ / 0.3 mmol / L NaHCO ３Flow rate: 1.5 mL / min. Detector: electrical conductivity detector. Injection volume: 20 μL.

[0244] <Photosensitive Resin Sheet> The photosensitive resin composition of the present invention is not limited in shape, and may be in the form of a sheet.

[0245] The photosensitive resin sheet of the present invention is obtained by forming the photosensitive resin composition of the present invention into a film on a support.

[0246] Specific methods for obtaining the photosensitive resin sheet of the present invention include, for example, applying a solvent-containing photosensitive resin composition to a support, drying at a temperature and time within a range that allows the solvent to volatilize, and (a) forming the resin into a sheet film in an incompletely cured state. From this perspective, it is preferable that the components other than the organic solvent used in the photosensitive resin composition of the present invention are soluble in a solvent, particularly an organic solvent. The support used for the photosensitive resin sheet is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The contact surface between the support and the photosensitive resin composition may be surface-treated with silicone, silane coupling agent, aluminum chelating agent, polyurea, or the like to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability. Furthermore, a protective film may be provided on the film surface to protect the surface of the photosensitive resin composition obtained by coating. This makes it possible to protect the surface of the film-like photosensitive resin composition from contaminants such as dust and dirt in the atmosphere.

[0247] Examples of methods for applying the photosensitive resin composition to a support include spin coating using a spinner, spray coating, roll coating, screen printing, a blade coater, a die coater, a calendar coater, a meniscus coater, a bar coater, a roll coater, a comma roll coater, a gravure coater, a screen coater, and a slit die coater. The film thickness after application varies depending on the application technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying be 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity, etc.

[0248] When a solvent is used, drying can be performed using an oven, a hot plate, infrared rays, or the like. The drying temperature and drying time may be within a range that allows the solvent to volatilize, and are preferably set appropriately within a range that allows the photosensitive resin composition to be in an uncured or semi-cured state. Specifically, drying is preferably performed within a range of 40°C to 150°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 80°C and 90°C for 2 minutes each.

[0249] <Cured Product> The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. That is, in the present invention, curing refers to the process of thermally baking the photosensitive resin composition.

[0250] As for the curing conditions, a temperature of 150°C to 320°C is applied to promote the thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment can be carried out by selecting a temperature and increasing the temperature stepwise, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but 170°C or higher is more preferable in order to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0251] <Method for producing a patterned cured film (1)> The method for producing a cured film on a substrate of the present invention includes the steps of: forming the photosensitive resin composition of the present invention into a film on a substrate; exposing the film of the photosensitive resin composition to light; developing the exposed film of the photosensitive resin composition; and curing the developed film of the photosensitive resin composition.

[0252] The patterned cured product thus obtained is a cured product mainly composed of resin, and has excellent heat resistance, electrical insulation properties, and mechanical properties.

[0253] The method for producing a cured product of the present invention includes a step of forming the photosensitive resin composition of the present invention into a film on a substrate.

[0254] The substrate on which the cured film is formed is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafer, ceramic deposition substrate, metal-plated substrate, sapphire, and gallium arsenide. Furthermore, electrical parts or elements such as electrical wiring, electrodes, semiconductor elements, and pixels made of light-emitting materials may be formed on these substrates.

[0255] The photosensitive composition of the present invention can be applied to a substrate by any known method, including, for example, a full-surface coating apparatus such as spin coating, dip coating, curtain flow coating, spray coating, or slit coating, or a printing apparatus such as screen printing, roll coating, microgravure coating, or inkjet printing.

[0256] After application, if a solvent is contained, a drying step is carried out to remove the solvent and form a film of the photosensitive resin composition. The drying step uses a vacuum drying device or a heating device such as a hot plate or oven. When a heating device is used, the drying step is preferably carried out at a temperature range of 50°C to 150°C for 30 seconds to 30 minutes. The thickness of the film of the photosensitive resin composition is preferably 0.1 mm to 100 μm.

[0257] The method for producing a cured product of the present invention includes a step of exposing the film of the photosensitive resin composition to light.

[0258] In the exposure step, the film-form photosensitive resin composition is exposed through a mask having a desired pattern to form a latent image. The wavelength of the exposure light is not particularly limited, and examples include light having a wavelength of 300 to 450 nm, such as g-line (436 nm), i-line (365 nm), and h-line (405 nm). Of these, light having a wavelength of 365 nm is preferred. Examples of light sources used in the exposure step include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, and metal halide lamps. Furthermore, the wavelength of the irradiated light may be adjusted, if necessary, through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a bandpass filter.

[0259] After exposure, post-exposure baking may be performed as necessary. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance for development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like can be used. The post-exposure baking temperature is preferably 50 to 170°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.

[0260] The method for producing a cured product of the present invention includes a step of developing the exposed film of the photosensitive resin composition.

[0261] To form a pattern of the photosensitive resin composition, after exposure, the exposed portion is removed using a developer, which may be an aqueous alkaline solution or an organic solvent in which an alkaline compound is dissolved.

[0262] Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, sodium carbonate, etc. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination to these aqueous alkaline solutions.

[0263] Specific examples of the organic solvent include polar solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as ethanol and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, and methyl isobutyl ketone.

[0264] After development, it is preferable to perform a rinse treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, examples of the organic solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, a hydrophilic organic solvent such as an alcohol such as ethanol or isopropyl alcohol, or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to the water for rinsing treatment.

[0265] The method for producing a cured product of the present invention includes a step of curing the developed film of the photosensitive resin composition.

[0266] After development, the resin is baked at a temperature of 150°C to 320°C, and if a crosslinking agent is used, a thermal crosslinking reaction is promoted, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0267] <Method for producing a patterned cured product film (2)> Another embodiment of the method for producing a cured product film on a substrate of the present invention includes the steps of pressing the photosensitive resin sheet of the present invention onto a substrate, and peeling off the support or protective film used in the photosensitive resin sheet to transfer a film of photosensitive resin composition onto the substrate, exposing the transferred film of photosensitive resin composition to light, developing the exposed film of photosensitive resin composition, and curing the developed film of photosensitive resin composition.

[0268] However, in this manufacturing method, the support or protective film used in the photosensitive resin sheet may be peeled off after exposure.

[0269] The patterned cured product thus obtained has excellent heat resistance, electrical insulation properties and mechanical properties.

[0270] The substrate on which the cured film is formed is not particularly limited, but examples include silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and these substrates on which circuit components are arranged. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth / epoxy copper-clad laminates, heat-resistant thermoplastic substrates such as polyetherimide substrates, polyetherketone substrates, and polysulfone substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit components include conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low-dielectric materials containing glass-based materials and / or resins, high-dielectric materials containing resins or high-dielectric-constant inorganic particles, and insulators containing glass-based materials.

[0271] The process of bonding the photosensitive resin sheet to the substrate is not particularly limited, but thermocompression bonding is preferably used, and known methods can be used. For example, when the photosensitive resin sheet has a protective film, the support is peeled off while leaving the protective film, and the photosensitive resin composition with the protective film is placed face to face with the substrate and bonded by thermocompression bonding. Thermocompression bonding can be performed by heat pressing, heat lamination, thermal vacuum lamination, etc. Among these, thermal lamination is preferred. The bonding temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, to prevent the resin composition film from curing during bonding, which would deteriorate the resolution of pattern formation in the exposure and development steps, the bonding temperature is preferably 150°C or lower.

[0272] The photosensitive resin sheet pressed onto the substrate is subjected to a process in which the support and the protective film, if any, are peeled off, and the photosensitive resin composition film on the substrate is exposed to light, the exposed portion of the exposed photosensitive resin composition film is removed and developed using a developer, and the developed photosensitive resin composition film is cured. These processes are not particularly limited, but are preferably carried out in the same manner as in the method (1) for producing a patterned cured film.

[0273] <Electronic Component> The electronic component of the present invention is an electronic component comprising a cured product obtained by curing the photosensitive resin composition of the present invention. The cured product obtained by curing the photosensitive resin composition of the present invention can be used in electronic components such as semiconductor devices. Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, and passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices or semiconductor packages. In the present invention, the term "semiconductor device" refers to any device that can function by utilizing the characteristics of a semiconductor element. Electro-optical devices in which a semiconductor element is connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these are all included in the semiconductor device category. Electronic components such as interposers for connecting semiconductor elements to a substrate are also included in the semiconductor device category. Specifically, since the cured product obtained by curing the photosensitive resin composition of the present invention has excellent electrical insulation properties, mechanical strength, adhesiveness, and heat resistance, it is preferable that the cured product be used as a surface protection film such as a passivation film or buffer coat film for a semiconductor element, an interlayer insulating film between rewirings formed on the surface of a semiconductor element, an insulating film between elements when multiple semiconductor elements are bonded, or an insulating film between wiring layers of a multilayer wiring board for high-density packaging or an interposer in a semiconductor device.

[0274] More preferably, the photosensitive resin composition of the present invention is cured and disposed as a semiconductor surface protective film or an interlayer insulating film between rewirings in a semiconductor device. By disposing a cured film of the photosensitive composition as a semiconductor surface protective film or an interlayer insulating film between rewirings, a highly reliable semiconductor device can be obtained.

[0275] More preferably, the semiconductor device has the rewiring and the interlayer insulating film repeatedly arranged in 2 to 10 layers. By repeatedly arranging the rewiring and the interlayer insulating film in 2 to 10 layers, the semiconductor device can be miniaturized.

[0276] Furthermore, the electronic component of the present invention preferably comprises the cured product of the present invention on a substrate. The surface of the substrate on which the cured product is formed can be appropriately selected depending on the application and process. Examples of the substrate include a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, ceramics, gallium arsenide, metal, and epoxy resin. A silicon substrate, a silicon carbide substrate, or a gallium nitride substrate is preferred, and a silicon carbide substrate or a gallium nitride substrate is more preferred.

[0277] <Display Device> The display device of the present invention is a display device including a first electrode formed on a substrate, an insulating layer formed on the first electrode so as to define pixels, and a second electrode provided opposite the first electrode, wherein the insulating layer is the cured product of the present invention. The insulating layer can be formed by applying and drying the photosensitive resin composition of the present invention onto a substrate on which the first electrode has been formed, or by laminating a sheet-like photosensitive resin composition, and then going through the steps of exposure, development, and curing to form a pattern of the insulating layer produced from the cured product of the present invention.

[0278] Another embodiment of the display device of the present invention is a display device comprising a thin film transistor (TFT) formed on a substrate and a planarizing film that covers irregularities on the substrate on which the TFT is formed, wherein the planarizing film is the cured product of the present invention.

[0279] Specifically, the display device preferably has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, with either or both of the planarization layer and the insulating layer being the cured product of the present invention. Taking an active matrix display device as an example, a substrate such as glass or a resin film has a TFT and wiring located on the sides of the TFT and connected to the TFT, a planarization layer on top of the TFT to cover the irregularities, and a display device is further provided on the planarization layer. The display device and the wiring are connected via contact holes formed in the planarization layer. The cured product obtained by curing the photosensitive resin composition of the present invention has excellent planarization properties and pattern dimensional stability, so it is preferably provided in a display device as a planarization layer. In particular, flexible display devices have become mainstream in recent years, and the display device may have a substrate having the driving circuit described above made of a resin film.

[0280] The present invention will be explained in more detail below by way of examples, but the present invention should not be construed as being limited to these specific examples. In addition, the names of the compounds used, for which abbreviations are used, are shown below.

[0281] (Monomers) OBBAC: 4,4'-oxybis(benzoyl chloride) ADC: adipic acid dichloride IPC: isophthaloyl dichloride CHAC: 1,4-cyclohexanedicarboxylic acid dichloride (cis, anti mixture) NDC: 1,5-naphthalenedicarboxylic acid dichloride ADDC: 1,3-adamantanedicarboxylic acid dichloride TCDC: 4,8-bis(chlorocarbonyl)tricyclo[5.2.1.0(2,6)]decane TDA: 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione MAAC: methacryloyl chloride BAC: benzoic acid chloride AP: 3-aminophenol SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane NDAH: 5-norbornene-2,3-dicarboxylic anhydride (protecting agent, catalyst) DCTB: di-tert-butyl dicarbonate IPVE: isopropyl vinyl ether DMAP: 4-dimethylaminopyridine TFA: trifluoroacetic acid (photosensitizer ((b) photosensitizer)) PAG-103: "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene, manufactured by BASF Japan Ltd.) NQD-1: naphthoquinone diazide sulfonic acid ester of 4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol (see Synthesis Example 114). NQD-2: naphthoquinone diazide sulfonic acid ester of 1,1,1-tris(4-hydroxyphenyl)ethane (see Synthesis Example 115). NQD-3: naphthoquinone diazide sulfonic acid ester of 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexanyl-1-ylidene]tetrakis[2-methylphenol] (see Synthesis Example 116).

[0282] (Others) Lutidine: 2,6-lutidine CP: cyclopentanone NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone MPA: 3-methoxy-N,N-dimethylpropanamide DMFDMA: N,N-dimethylformamide dimethyl acetal HMOM: HMOM-TPPHBA (manufactured by Honshu Chemical Industry Co., Ltd.): a compound represented below having three aromatic rings in the molecule to which two methoxymethyl groups, which are thermally crosslinkable groups, are bonded)

[0283]

[0284] (1) Weight-average molecular weight of resin Measurement was performed using a gel permeation chromatography (GPC) analyzer under the following conditions: Measurement device: Waters 2695 (manufactured by Waters Corporation) Column temperature: 50°C Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21% by mass of lithium chloride and 0.48% by mass of phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).

[0285] (2) Content of fluorine atoms in the total resin in the photosensitive resin composition: The resin was separated from the photosensitive resin composition using high-performance liquid chromatography, and the separated resin was precisely weighed as a sample. Using the automatic sample combustion apparatus described below, the resin was combusted in a combustion tube of an analyzer. The generated gas was absorbed in the following absorption liquid, and a portion of the absorption liquid after absorption was analyzed by ion chromatography. The resin mass was taken as 100% by mass, and the mass of fluorine atoms relative to this was calculated as a percentage (mass%).

[0286] <Resin separation conditions> System: LC-10Avp series manufactured by Shimadzu Corporation Detector: Photodiode array detector (UV=254 nm) Flow rate: 1 mL / min Column temperature: 50°C Mobile phase: NMP (containing 0.21% by mass of lithium chloride and 0.48% by mass of phosphoric acid) The column to be used is selected based on the properties of the resin and is capable of performing separation.

[0287] <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C Outlet 1000°C Gas: Ar / O ２ 200mL / min :O ２ / 400 mL / min Absorption liquid: H ２ O ２ 0.036 mass%, internal standard P 4 μg / mL Amount of absorption solution: 20 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DINONEX Co., Ltd.) Mobile phase: 2.7 mmol / L Na ２ CO ３ / 0.3 mmol / L NaHCO ３ Flow rate: 1.5 mL / min. Detector: electrical conductivity detector. Injection volume: 20 μL.

[0288] (3) Protection Rate, Capping Rate of Main Chain Ends (a) The protection rate of the resin was measured using a 400 MHz, 1H-NMR (nuclear magnetic resonance) spectrometer (AL-400 manufactured by JEOL Ltd.). Specifically, the measurement was performed 16 times in a deuterated dimethyl sulfoxide solution. The protection rate was calculated using the following formula, where M is the integral value of the protons of the phenolic hydroxyl groups observed in the vicinity of 9 ppm to 11 ppm in the resin before protection, and N is the integral value of the protons of the phenolic hydroxyl groups observed in the vicinity of 9 ppm to 11 ppm in the resin after protection.

[0289] Protection rate (mol %) = (M - N) / M x 100. (a) The capping rate of the main chain ends of the resin was measured using the same apparatus, deuterated solvent, and cumulative number of measurements as used to calculate the protection rate. When the theoretical integral of protons attributable to the functional group specific to the terminal structure when 100% of the main chain ends are reacted with the terminal capping agent is defined as H1, and the integral of protons attributable to the same functional group as above actually observed is defined as H2, the capping rate of the main chain ends can be calculated using the following formula:

[0290] Capping rate of main chain ends (mol %)=H2 / H1×100.

[0291] (4) Solid Content Concentration The solid content concentration of the photosensitive resin composition was determined by the following method. 1.5 g of the solution was weighed into an aluminum cup and heated at 180°C for 30 minutes using a hot plate to evaporate the liquid. The mass of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration was determined from the ratio to the mass before heating.

[0292] (5) Contents of the compound represented by formula (16), the compound represented by formula (30), and the compound represented by formula (31) The photosensitive resin composition sample was subjected to GC-MS analysis using a GC-MS device (manufactured by Agilent) under the following conditions: column temperature: 40 to 300°C, carrier gas: helium (1.5 mL / min), scan range: m / z 29 to 600. Each target compound was subjected to GC-MS analysis under the same conditions as above to create a calibration curve, and the content of the compound in the sample was calculated.

[0293] (6) Preparation of Relief Pattern Twelve hours after the preparation of the photosensitive resin composition, the composition was spin-coated onto an 8-inch silicon wafer using an ACT-8 coater / developer (Tokyo Electron Limited), and heated at 100°C for 2 minutes to prepare a 4.0 μm-thick film of the photosensitive resin composition. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. Thereafter, the film was exposed to light at an exposure dose of 5 to 300 mJ / cm using an i-line stepper NSR-2005i9C (Nikon Corporation) through a mask having a 10 μm contact hole pattern. ２ in the range of 5 mJ / cm ２ One hour after the exposure, the film was developed using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH, manufactured by Tama Chemicals Co., Ltd.) as the developer, and the development time was adjusted so that the film thickness loss in the unexposed areas before and after development was 0.5 μm. After development, the film was rinsed with distilled water and then shaken off and dried to obtain a relief pattern.

[0294] (7) Sensitivity Evaluation The relief pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the sensitivity (Eth(1)). The results were evaluated as follows, and a sensitivity of 500 mJ / cm was obtained. ２ A++, A+, A, B+, B and C, which are less than 10%, were rated as passing. A is the most excellent.

[0295] A++: Sensitivity is 50 mJ / cm ２ A+: Sensitivity is less than 50 mJ / cm ２ More than 80mJ / cm ２ A: Sensitivity is less than 80 mJ / cm ２ 120mJ / cm or more ２ B+: Sensitivity is less than 120 mJ / cm ２ 160mJ / cm or more ２ B: Sensitivity is less than 160 mJ / cm ２ More than 200mJ / cm ２ C: Sensitivity is less than 200 mJ / cm ２ More than 500mJ / cm ２ D: Sensitivity is less than 500 mJ / cm ２ More than 1000mJ / cm ２ E: Sensitivity is less than 1000 mJ / cm ２ That's all.

[0296] (8) Solubility in Solvent Solubility in solvent was evaluated as follows. A solvent prepared by mixing propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether in a mass ratio of 7:3 was used. The photosensitive resin composition sample was applied to an 8-inch silicon wafer by spin coating using an ACT-8 coater / developer (manufactured by Tokyo Electron Limited), and heated at 100°C for 2 minutes to produce a 4.0 μm-thick film of the photosensitive resin composition. The film thickness was measured using a Lambda Ace STM-602 optical interference film thickness measuring device (manufactured by SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. The sample was then immersed in the thinner for 60 seconds. The silicon wafer was observed for the presence or absence of residue remaining on it.

[0297] The results were evaluated as follows, and A+, A, B, and C, which indicate that the area of ​​the residue remaining on the silicon wafer is less than 20%, were considered to be acceptable. A+ is the best.

[0298] A+: The area where residues exist is less than 2%. A: The area where residues exist is 2% or more but less than 5%. B: The area where residues exist is 5% or more but less than 10%. C: The area where residues exist is 10% or more but less than 20%. D: The area where residues exist is 20% or more but less than 30%. E: The area where residues exist is 30% or more.

[0299] (9) Evaluation of Development Residues In the same manner as in (6) above, the photosensitive resin composition was applied onto an ITO (indium tin oxide) substrate and prebaked by heating at 100°C for 2 minutes to prepare a film of the photosensitive resin composition with a film thickness of approximately 1.8 µm. This film was exposed to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp at a dose of 150 mJ / cm using a manual exposure machine (MA-1200; manufactured by Japan Science Research Institute Co., Ltd.) through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International, Inc.; having a 2-50 μm, 1:1 line and space pattern, each having areas with transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and 60%). ２ (value measured by an i-line illuminometer), the film was developed, rinsed, and dried to prepare a developed film of the photosensitive resin composition. The development time was adjusted so that the film thickness loss in the unexposed area before and after development was 0.5 μm, and rinsing was performed using deionized water.

[0300] Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolved pattern of the prepared developed film was observed to check for the presence or absence of residue in the openings of a 20 μm line-and-space pattern at the location of the minimum exposure dose where the opening width was the same line width (20 μm) as the mask design. The results were evaluated as follows, and grades A, B, C, and D, which indicate that the area of ​​residue in the openings was less than 10%, were judged to be acceptable. Grade A is the most favorable result. A: The area of ​​residue in the openings was less than 2%. B: The area of ​​residue in the openings was 2% or more but less than 5%. C: The area of ​​residue in the openings was 5% or more but less than 10%. D: The area of ​​residue in the openings was 10% or more but less than 20%. E: The area of ​​residue in the openings was 20% or more.

[0301] (10) Pattern Dimensional Accuracy A relief pattern was prepared in the same manner as in (6) above. The contact hole opening diameter of the resulting relief pattern was measured in the same manner as in (7) above. The dimension L1 of the 10 μm pattern in Eth(1) was measured, and the dimensional accuracy L (%) was calculated using the following formula relative to the mask dimension of the 10 μm pattern. Evaluation was performed according to the following criteria, with A+ to C being considered acceptable. A+ is the most favorable result. Dimensional accuracy L (%) = L1 / 10 × 100. A+: L is less than 102. A: L is 102 or more but less than 104. B+: L is 104 or more but less than 106. B: L is 106 or more but less than 108. C: L is 108 or more but less than 115. D: L is 115 or more.

[0302] (11) Effect of leaving after exposure A relief pattern was prepared in the same manner as in (6) above, except that the pattern was left for 24 hours in an environment of 23°C and 45% RH after exposure. The contact hole opening diameter of the obtained relief pattern was measured in the same manner as in (7) above, and the minimum exposure dose at which the contact hole opening diameter reached 10 μm was calculated as Eth(2). The sensitivity change y1 (%) was calculated using the Eth(1) calculated in (7) above and the following formula, and the result was evaluated according to the following criteria, with A+ to B being considered acceptable. A+ is the most preferable result. Sensitivity change y1 (%) = Eth(2) / Eth(1) × 100 A+: Sensitivity change y1 is less than 110 A: Sensitivity change y1 is 110 or more and less than 130 B+: Sensitivity change y1 is 130 or more and less than 150 B: Sensitivity change y1 is 150 or more and less than 200 C+: Sensitivity change y1 is 200 or more and less than 250 C: Sensitivity change y1 is 250 or more.

[0303] (12) Shrinkage of the film after curing A sample photosensitive resin composition was applied by spin coating onto an 8-inch silicon wafer using an ACT-8 coater / developer (Tokyo Electron Limited), and heated at 100°C for 2 minutes to produce a 4.0 μm-thick film of the photosensitive resin composition. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. The resin film-coated wafer was heat-treated at 250°C for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less) using a clean oven (KOYO THERMO SYSTEMS CO., LTD. CLH-21CD-S), and the film thickness R (μm) was measured. The value of R / 4×100 was taken as the film thickness retention after curing. The higher the film thickness retention, the less shrinkage during heat treatment, which is considered to be a favorable result.

[0304] The results were judged as follows, with A+ to C+ being considered acceptable, with A+ being the most favorable result. A+: Film thickness retention rate of 85% or more A: Film thickness retention rate of 82% or more but less than 85% B+: Film thickness retention rate of 78% or more but less than 82% B: Film thickness retention rate of 75% or more but less than 78% C+: Film thickness retention rate of 70% or more but less than 75% C: Film thickness retention rate less than 70%.

[0305] (13) Sensitivity Change During Storage at Room Temperature A relief pattern was prepared in the same manner as in (6) above, except that the composition was left to stand for 7 days in an environment of 23°C and 45% RH after preparation before coating. The contact hole opening diameter of the resulting relief pattern was measured in the same manner as in (7) above, and the minimum exposure dose at which the contact hole opening diameter reached 10 μm was determined as Eth(3). The sensitivity change y2 (%) was calculated using the Eth(1) calculated in (7) above and the following formula, and the result was evaluated according to the following criteria, with A+ to C+ being considered acceptable. A+ is the most preferable result. Sensitivity change y2 (%) = Eth(3) / Eth(1) × 100 A+: Sensitivity change y2 is less than 110 A: Sensitivity change y2 is 110 or more and less than 130 B+: Sensitivity change y2 is 130 or more and less than 150 B: Sensitivity change y2 is 150 or more and less than 200 C+: Sensitivity change y2 is 200 or more and less than 250 C: Sensitivity change y2 is 250 or more.

[0306] Synthesis Example 1: Synthesis of diamine (DAP-A) A 500 ml four-neck flask equipped with a stirrer, thermocouple, and dropping funnel was charged with 24.28 g (0.086 mol) of BisP-3MZ (4,4'-(3-methylcyclohexane-1,1-diyl)diphenol, manufactured by Honshu Chemical Industry Co., Ltd.) and 100 ml of glacial acetic acid, and the mixture was stirred. The internal temperature was raised to 50°C in a water bath. To this mixture, 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour, followed by ice cooling to lower the internal temperature to 13°C, and then 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was continued for 3 hours, and the precipitated yellow crystals were filtered, washed successively with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain the dinitro form.

[0307] Next, 50.27 g (0.135 mol) of the dinitro compound, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were placed in a 2 L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and the mixture was stirred under ice cooling. 0.90 g of 5% palladium-carbon (Wako Pure Chemical Industries, Ltd.) suspended in 30 ml of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 ml of ethanol. All of the solvent was removed by heating under reduced pressure, and the residue was washed with 75 ml of ice-cold ethanol, filtered, and then washed with 75 ml of deionized water and 150 ml of diethyl ether, followed by drying under reduced pressure, to obtain diamine (DAP-A).

[0308] Synthesis Example 2: Synthesis of diamine (DAP-B) A dinitro product was synthesized using 26.70 g (0.086 mol) of BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4′-(3,3,5-trimethylcyclohexylidene)bisphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-B) was obtained in the same manner as in Synthesis Example 1, except that 54.06 g (0.135 mol) of the dinitro product was used.

[0309] Synthesis Example 3: Synthesis of diamine (DAP-C) A dinitro product was synthesized using 23.25 g (0.086 mol) of 4,4′-(1,3-dimethylbutylidene)diphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-C) was obtained in the same manner as in Synthesis Example 1, except that 48.65 g (0.135 mol) of the dinitro product was used.

[0310] Synthesis Example 4: Synthesis of diamine (DAP-D) A dinitro product was synthesized using 20.84 g (0.086 mol) of 2,2-bis(4-hydroxyphenyl)butane (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-D) was obtained in the same manner as in Synthesis Example 1 except that 44.86 g (0.135 mol) of the dinitro product was used.

[0311] Synthesis Example 5: Synthesis of diamine (DAP-E) A dinitro product was synthesized using 25.66 g (0.086 mol) of BisP-IOTD (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4′-(2-ethylhexylidene)diphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-E) was obtained in the same manner as in Synthesis Example 1, except that 52.44 g (0.135 mol) of the dinitro product was used.

[0312] Synthesis Example 6: Synthesis of diamine (DAP-F) A dinitro product was synthesized using 22.13 g (0.086 mol) of BisP-IBTD (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4′-(2-methylpropane-1,1-diyl)diphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-F) was obtained in the same manner as in Synthesis Example 1, except that 46.89 g (0.135 mol) of the dinitro product was used.

[0313] Synthesis Example 7: Synthesis of diamine (DAP-G) A dinitro compound was synthesized using 20.84 g (0.086 mol) of BIOC-E (manufactured by Asahi Organic Chemicals Co., Ltd.; 1,1′-bis(4-hydroxy-3-methylphenyl)methane) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-G) was obtained in the same manner as in Synthesis Example 1, except that 44.86 g (0.135 mol) of the dinitro compound was used.

[0314] Synthesis Example 8: Synthesis of diamine (DAP-H) A dinitro compound was synthesized using 23.08 g (0.086 mol) of 4,4′-cyclohexylidenebisphenol instead of Bis-Z (manufactured by Honshu Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-H) was obtained in the same manner as in Synthesis Example 1, except that 48.38 g (0.135 mol) of the dinitro compound was used.

[0315] Synthesis Example 9: Synthesis of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-4-methylpentane (DAP-CHA) 15.00 g (0.050 mol) of DAP-C obtained in Synthesis Example 3 was dissolved in 100 mL of acetone and 17.40 g (0.300 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the solution was cooled to −15°C. To this solution, a solution prepared by dissolving 20.40 g (0.110 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was stirred at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and dried in vacuo at 50°C.

[0316] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2.0 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain diamine (DAP-CHA).

[0317] Synthesis Example 10: Synthesis of Resin (POL-01) Under a dry nitrogen stream, 31.24 g (100 mmol) of DAP-A was dissolved in 140 g of MPA in a three-neck flask. The solution was then cooled to -15°C. After confirming that the solution temperature had reached -15°C, 22.13 g (0.075 mol) of 4,4'-oxybisbenzoic acid chloride was added along with 25 g of MPA. After stirring at -10°C for 30 minutes, the solution was heated to 20°C and stirred for an additional 2 hours. The solution was again cooled to -15°C. After confirming that the solution temperature had reached -15°C, 5.23 g (0.050 mol) of methacryloyl chloride was added along with 10 g of MPA. After the dropwise addition was completed, stirring was continued for 2 hours at 20°C. After the reaction was completed, the solution was poured into 2 liters of pure water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a resin (POL-01). The weight-average molecular weight Mw of the obtained resin was 20,700, and the fluorine atom content was 0% by mass. The blocking rate of the main chain ends was 85%. The evaluation results are shown in Table 1.

[0318] Synthesis Examples 11 to 40: Synthesis of Resins (POL-02 to POL-31) Synthesis was performed in the same manner as in Synthesis Example 10, except that the types and amounts of dicarboxylic acid chloride, diamine, carboxylic acid chloride, and solvent were changed as shown in Table 1. The results are shown in Table 1.

[0319] Synthesis Example 41: Synthesis of Resin (POL-32) Under a dry nitrogen stream, 28.94 g (0.085 mol) of DAP-B was dissolved in 140 g of MPA in a three-neck flask. The solution was then cooled to -15°C. After confirming that the solution temperature had reached -15°C, 29.51 g (0.100 mol) of 4,4'-oxybisbenzoic acid chloride was added along with 25 g of MPA. After stirring at -10°C for 30 minutes, the solution was warmed to 20°C and stirred for an additional 2 hours. The solution was again cooled to -15°C. After confirming that the solution temperature had reached -15°C, 3.27 g (0.030 mol) of 3-aminophenol was added along with 10 g of MPA. After the dropwise addition was completed, stirring was continued for 2 hours at 20°C. After the reaction was completed, the solution was poured into 2 liters of pure water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a resin (POL-32). The weight-average molecular weight Mw of the obtained resin was 24,100, and the fluorine atom content was 0% by mass. The blocking rate of the main chain ends was 87%. The evaluation results are shown in Table 1.

[0320] Synthesis Examples 42 to 44: Synthesis of Resins (POL-33 to POL-35) Synthesis was performed in the same manner as in Synthesis Example 41, except that the types and amounts of dicarboxylic acid chloride, diamine, monoamine, and solvent were changed as shown in Table 1. The results are shown in Table 1.

[0321] Synthesis Example 45: Synthesis of Resin (POL-36) Under a dry nitrogen stream, 34.05 g (0.100 mol) of DAP-B was dissolved in 140 g of MPA in a three-neck flask. The solution was then cooled to -15°C. After confirming that the solution temperature had reached -15°C, 23.61 g (0.080 mol) of 4,4'-oxybisbenzoic acid chloride was added along with 25 g of MPA. After stirring for 30 minutes at -10°C, the solution was warmed to 20°C and stirred for an additional 2 hours. Then, 6.57 g (0.040 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added along with 10 g of MPA. After the dropwise addition was completed, stirring was continued for 2 hours at 20°C. After the reaction was completed, the solution was poured into 2 liters of pure water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a resin (POL-34). The weight-average molecular weight Mw of the obtained resin was 22,400, and the fluorine atom content was 0% by mass. The blocking rate of the main chain ends was 80%. The evaluation results are shown in Table 1.

[0322] Synthesis Example 46: Synthesis of Resin (POL-37) Synthesis was performed in the same manner as in Synthesis Example 45, except that the types and amounts of dicarboxylic acid chloride, diamine, acid anhydride, and solvent were changed as shown in Table 1. The results are shown in Table 1.

[0323] Synthesis Example 47: Synthesis of Resin (POL-38) Under a dry nitrogen stream, 22.35 g (0.042 mol) of DAP-CHA and 0.62 g (0.0025 mol) of SiDA were dissolved in 95 g of MPA in a three-neck flask. To this was added 15.00 g (0.050 mol) of TDA along with 10 g of MPA, and the mixture was stirred at 60°C for 2 hours. Then, 1.09 g (0.010 mol) of AP was added as an end-capping agent along with 10 g of MPA, and the mixture was allowed to react at 60°C for 1 hour. After the temperature was lowered from 60°C to 40°C, a solution prepared by diluting 11.90 g (0.010 mol) of DMFDMA with 10 g of MPA was added dropwise. After the dropwise addition, stirring was continued at 40°C for 2 hours. After stirring was completed, the solution was poured into 2 L of deionized water, and the polymer solid precipitate was collected by filtration. The polymer solid was then washed three times with 2 L of deionized water and dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyamic acid ester (POL-38), which is a form of polyimide.

[0324]

[0325]

[0326] Synthesis Example 48: Synthesis of Resin (POL-01-BOC20) In a dry nitrogen stream, 8.00 g of POL-01 was dissolved in 40 g of MPA in a three-neck flask as a base polymer. Then, 1.36 g (6.20 mmol) of di-tert-butyl dicarbonate and 0.095 g (0.900 mmol) of 4-dimethylaminopyridine were added, and the mixture was allowed to react at 20°C for 1 hour. After completion of the reaction, the solution was poured into 500 mL of pure water to precipitate a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain Resin (POL-01-BOC20). The proportion of phenolic hydroxyl groups protected with acid-decomposable groups (protection rate) was 20 mol%. The results are shown in Table 2.

[0327] Synthesis Examples 49 to 57, 68 to 92: Synthesis of Resins (POL-02-BOC20 to POL-10-BOC20, POL-11-BOC20 to POL-29-BOC20, POL-32-BOC20 to POL-37-BOC20) Synthesis was performed in the same manner as in Synthesis Example 48, except that the amounts of the base polymer, protecting agent, and catalyst were changed to those shown in Table 2. The results are shown in Table 2.

[0328]

[0329]

[0330] Synthesis Example 58: Synthesis of Resin (POL-01-ACT40) Under a dry nitrogen stream, 10.00 g of POL-01 as a base polymer and 30 g of CP as a solvent were weighed and dissolved in a three-necked flask. 2.69 g (0.031 mmol) of isopropyl vinyl ether as a protective agent was added thereto, and the mixture was stirred at 0°C for 1 hour. Next, 0.44 g (3.85 mmol) of trifluoroacetic acid as a catalyst was added, and the mixture was stirred at 0°C for 3 hours. After stirring was completed, the acid catalyst was neutralized with a saturated aqueous sodium bicarbonate solution, and the water bath was then removed. The organic layer was further washed twice with water. Thereafter, low-boiling point residues were removed using a rotary evaporator in order to remove unreacted isopropyl vinyl ether. The solids concentration of the solution was then measured, and CP was added to bring the solids content to 40%, yielding a 40% solids solution of a resin (POL-01-ACT40) in which hydroxyl groups were protected with 1-isopropoxyethyl groups, which are acid-decomposable groups. The proportion of phenolic hydroxyl groups protected with acid-decomposable groups (protection rate) was 42 mol%. The results are shown in Table 2.

[0331] <Synthesis Examples 59 to 67, 93 to 117: Synthesis of Resins (POL-02-ACT40 to POL-10-ACT40, POL-11-ACT40 to POL-29-ACT40, POL-32-ACT40 to POL-37-ACT40)> Resins were synthesized in the same manner as in Synthesis Example 58, except that the amounts of the base polymer, protective agent, and catalyst were changed to those shown in Table 2. The results are shown in Table 2.

[0332] Synthesis Example 118 Synthesis of NQD-1 Under a dry nitrogen stream, 21.22 g (0.050 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. To this solution, a solution prepared by dissolving 15.18 g of triethylamine in 50 g of 1,4-dioxane was added dropwise so that the temperature in the system was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Filtration was then performed, and the resulting precipitate was collected. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound NQD-1 shown in the following formula. The esterification rate was 90 mol%.

[0333]

[0334] * indicates the bonding site with the oxygen atom.

[0335] Synthesis Example 119 Synthesis of NQD-2 Under a dry nitrogen stream, 15.32 g (0.050 mol) of TrisP-HAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 22.84 g (0.085 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. To this solution, a solution prepared by dissolving 9.56 g of triethylamine in 50 g of 1,4-dioxane was added dropwise so that the temperature in the system was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Filtration was then performed, and the resulting precipitate was collected. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound NQD-2 shown in the following formula. The esterification rate was 57 mol%.

[0336]

[0337] * indicates the bonding site with the oxygen atom.

[0338] Synthesis Example 120 Synthesis of NQD-3 Under a dry nitrogen stream, 31.64 g (0.050 mol) of TekOC-4HBPA (manufactured by Honshu Chemical Industry Co., Ltd.) and 51.05 g (0.190 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 550 g of 1,4-dioxane and the temperature was brought to room temperature. To this solution, a solution prepared by dissolving 21.36 g of triethylamine in 50 g of 1,4-dioxane was added dropwise so that the temperature in the system was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Filtration was then performed, and the resulting precipitate was collected. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound NQD-3 shown in the following formula. The esterification rate was 95 mol%.

[0339]

[0340] * indicates the bonding site with the oxygen atom.

[0341] Example 1 Under yellow light, (a) 1.0 g of POL-01 as a resin, (b) 0.80 g of NQD-1 synthesized in Synthesis Example 118 as a photosensitizer, and 4.0 g of GBL as a solvent were mixed and stirred to prepare a photosensitive resin composition.

[0342] The prepared photosensitive resin compositions were evaluated for (7) sensitivity, (8) solubility in solvents, (9) development residue, (10) pattern dimensional accuracy, (11) effect of leaving after exposure, (12) shrinkage of the film after curing, and (13) change in sensitivity during storage at room temperature. The results are shown in Table 3.

[0343] Examples 2 to 53 and Comparative Examples 1 to 4 Resin compositions were prepared and evaluated in the same manner as in Example 1, except that the composition of each component of the photosensitive resin composition was changed as shown in Table 3. The results are shown in Table 3.

[0344]

[0345]

[0346]

[0347]

[0348] *1: Content (mass %) of the compound represented by formula (16) contained in the composition *2: Content (mass %) of the compound represented by formula (30) and the compound represented by formula (31) contained in the composition Example 54 Under yellow light, (a) 1.00 g of POL-01-BOC20 as a resin, (b) 0.40 g of NQD-1 synthesized in Synthesis Example 118 as a photosensitizer, and 4.0 g of GBL as a solvent were added and stirred to prepare a photosensitive resin composition.

[0349] The prepared photosensitive resin compositions were evaluated for (7) sensitivity, (8) solubility in solvents, (9) development residue, (10) pattern dimensional accuracy, (11) effect of exposure time, (12) shrinkage of the cured film, and (13) change in sensitivity during storage of the solution at room temperature. The results are shown in Table 4.

[0350] Examples 55 to 61, 70 to 110, Comparative Examples 5 to 6, 9 to 10 Resin compositions were prepared and evaluated in the same manner as in Example 54, except that the formulation of each component of the photosensitive resin composition was changed as shown in Table 4. The results are shown in Table 4.

[0351] Example 62 Under yellow light, (a) 2.50 g of a 40% solids CP solution of POL-01-ACT40 as a resin, and (b) 0.15 g of PAG-103 and 0.005 g of lutidine as photosensitizers were added and stirred. Then, 1.50 g of CP was added to adjust the concentration, thereby preparing a photosensitive resin composition.

[0352] The prepared photosensitive resin compositions were evaluated for (7) sensitivity, (8) solubility in solvents, (9) development residue, (10) pattern dimensional accuracy, (11) effect of exposure time, (12) shrinkage of the cured film, and (13) change in sensitivity during storage of the solution at room temperature. The results are shown in Table 4.

[0353] Examples 63 to 69, 111 to 141, Comparative Examples 7 to 8, 11 to 12 Resin compositions were prepared and evaluated in the same manner as in Example 62, except that the formulation of each component of the photosensitive resin composition was changed as shown in Table 4. The evaluation results are shown in Table 4.

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360] *1: Content (mass%) of the compound represented by formula (16) contained in the composition *2: Content (mass%) of the compound represented by formula (30) and the compound represented by formula (31) contained in the composition

Claims

1. A photosensitive resin composition containing (a) a resin containing a repeating unit represented by formula (13) (hereinafter simply referred to as "(a) resin") and (b) a photosensitizer. (R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-decomposable group having 1 to 120 carbon atoms. U represents a tetravalent organic group having 1 to 120 carbon atoms, and Y represents a divalent organic group having 1 to 120 carbon atoms, and one or both of U and Y include a structure selected from the group consisting of formula (2), formula (3), formula (14), and formula (15). (In formula (2), R ５ is the number of carbon atoms m １ is a cycloalkane-1,1-diyl group of the formula R ８ is a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) in the group, and when there are multiple groups, they may be the same or different. １ is an integer between 4 and 7, n １ is 1 to 2 m １ is an integer equal to or less than -2. ５ - (R ８ ) n １ is m １ If is even, then [m １ / 2+1] and the line connecting the carbon at the 1st position, m １ If is odd, then [(m １ +1) / 2] and the carbon at [(m １ The structure does not have line symmetry with respect to the line connecting the midpoint of the bond between the carbon atoms at positions [+1] / [2+1] and the carbon atom at position 1. * represents a bonding point. ６ and R ７ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group). ６ and R ７ do not have the same structure. * represents a bonding point. In formula (14) and formula (15), R ９ each independently represents an alkyl group having 1 to 4 carbon atoms. * represents a point of attachment.

2. The photosensitive resin composition according to claim 1, wherein in formula (13), U is a tetravalent organic group having 1 to 120 carbon atoms containing a structure selected from the group consisting of formulas (2), (3), (14), and (15), and Y is a divalent organic group having 1 to 120 carbon atoms which may contain a structure selected from the group consisting of formulas (2), (3), (14), and (15).

3. The photosensitive resin composition according to claim 2, wherein all or part of the repeating units represented by formula (13) are repeating units represented by formula (1). (R １ and R ２ The explanation given in equation (13) is used. ３ and R ４ each independently represents an alkyl group having 1 to 4 carbon atoms, m ２ and n ２ each independently represents an integer of 0 to 3. X represents a structure selected from the group consisting of formula (2) and formula (3), and V represents a divalent organic group having 1 to 120 carbon atoms which may contain a structure selected from the group consisting of formula (2) and formula (3).

4. The photosensitive resin composition according to claim 3, wherein V in formula (1) is a divalent aromatic group having 6 to 50 carbon atoms, a linear or branched divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 9 carbon atoms, or a divalent group having an adamantane skeleton.

5. m in the formula (1) ２ and n ２ The photosensitive resin composition according to claim 3 , wherein is 0.

6. The photosensitive resin composition according to any one of claims 1 to 5, which does not contain a compound represented by formula (16), or if it contains one, the content thereof is 0.3 mass% or less when the total amount of the photosensitive resin composition is taken as 100 mass%. (In formula (16), R １０ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R １１ When a plurality of groups are present, each independently represents a monovalent organic group having 1 to 12 carbon atoms, s represents an integer of 2 or 3, and t represents an integer satisfying 0≦t≦(s+1).

7. A photosensitive resin composition according to any one of claims 1 to 5, wherein the resin (a) has a thermally crosslinkable group or a phenolic hydroxyl group at at least one of the molecular chain terminals.

8. A photosensitive resin composition according to any one of claims 1 to 5, wherein the resin (a) has a structure represented by formula (17) at at least one of the molecular chain terminals. (In formula (17), R １２ represents an organic group having 1 to 30 carbon atoms. * represents a bonding point.

9. In the formula (17), R １２ The photosensitive resin composition according to claim 8 , wherein 10. In the formula (3), R ６ and R ７ The photosensitive resin composition according to any one of claims 1 to 5, which satisfies the following condition 1 or condition 2: Condition 1: R ６ and R ７ One of R is a hydrogen atom, and the other is a hydrocarbon group having 2 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) in the group. ６ and R ７ are hydrocarbon groups having 1 to 10 carbon atoms which may contain an ether bond or a carbonyl group (ketone group) within the group. ６ and R ７ are not identical structures.) 11. In the formula (3), R ６ and R ７ The photosensitive resin composition according to claim 10, which satisfies condition 2.

12. In the formula (2), R ８ The total number of carbon atoms in R is 1 or more and 5 or less, and ６ and R ７ The photosensitive resin composition according to any one of claims 1 to 5, wherein the total number of carbon atoms in 13. The photosensitive resin composition according to any one of claims 1 to 5, wherein the structure represented by formula (2) is any one of the structures represented by formulas (2-1) to (2-4). (In formula (2-1), R １３ ~R １８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １３ ~R １４ The total number of carbon atoms in R １７ ~R １８ The total number of carbon atoms in the formula (2-2) is not equal. １９ ~R ２８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ The total number of carbon atoms in the formula (2-3) is not equal. ２９ ~R ３６ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２９ ~R ３２ The total number of carbon atoms in R ３３ ~R ３６ The total number of carbon atoms in the formula (2-4) is not equal. ３７ ~R ４８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ３７ ~R ４２ The total number of carbon atoms in R ４３ ~R ４８ The total number of carbon atoms is not equal.) 14. The photosensitive resin composition according to claim 3, wherein X in formula (1) is a group represented by any one of formulas (5) to (12) and formulas (18) to (24). (* indicates a point of attachment.) 15. The photosensitive resin composition according to claim 4, wherein the divalent aromatic group having 6 to 50 carbon atoms represented by V in formula (1) is a group represented by either formula (25) or formula (26). (R ４９ ~R ５２ each independently represents a halogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. d and e each independently represent an integer of 0 to 4, f represents an integer of 1 to 3, and g and h each independently represent an integer of 0 to 3. Z represents a single bond, an ether group, a thioether group, a sulfone group, a ketone group, or a linear or branched alkylene group having 1 to 10 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. * represents a bonding point.

16. The photosensitive resin composition according to claim 4, wherein the divalent alicyclic group having 3 to 9 carbon atoms represented by V in formula (1) is a group represented by any one of formulas (27) to (29). (R ５３ ~R ５５ each independently represents a halogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. i represents an integer of 0 to 2, j represents an integer of 0 to 3, and k represents an integer of 0 to 3. * represents a bonding point. However, all R ５３ The total number of carbon atoms contained in R is 5 or less, and all R ５４ The total number of carbon atoms contained in R is 4 or less, and all R ５５ The total number of carbon atoms contained in is 3 or less.) 17. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound represented by formula (30) or a compound represented by formula (31), the content of which is 0.01 to 90 mass % when the total amount of the photosensitive resin composition is 100 mass %. (R ５６ each independently represents an alkyl group having 1 to 6 carbon atoms; R ５７ represents an alkyl group having 2 to 6 carbon atoms.

18. The photosensitive resin composition according to any one of claims 1 to 5, wherein all or part of the (b) photosensitizer is a compound represented by formula (32). (R ５８ represents a trivalent to hexavalent alicyclic or aliphatic group having 1 to 20 carbon atoms; R ５９ When a plurality of Q's are present, each independently represents a monovalent aliphatic group having 1 to 6 carbon atoms. When a plurality of Q's are present, each independently represents a hydrogen atom, a 1,2-naphthoquinonediazide-4-sulfonyl group, or a 1,2-naphthoquinonediazide-5-sulfonyl group, provided that not all of them are hydrogen atoms. P1 represents an integer of 0 to 4, P2 represents an integer of 1 to 5, and P1+P2 is an integer of 1 to 5. q represents an integer of 3 to 6.

19. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound having, in the molecule, 3 to 6 aromatic rings to which one or more thermally crosslinkable groups are bonded.

20. (a) The resin contains R as the repeating unit represented by formula (1). １ and R ２ 4. The photosensitive resin composition according to claim 3, wherein either or both of the repeating units are an alkyl group having 1 to 6 carbon atoms or a monovalent acid-decomposable group having 1 to 120 carbon atoms.

21. A photosensitive resin composition according to any one of claims 1 to 5, wherein the amount of fluorine atoms bonded to the molecular structure of the resin is less than 2 mass % when the total mass of the resin contained in the photosensitive resin composition is 100 mass %.

22. The photosensitive resin composition according to any one of claims 1 to 5, further comprising, as a resin other than the (a) resin, a resin containing at least one selected from the group consisting of a repeating unit represented by formula (33), a repeating unit represented by formula (34), and a repeating unit represented by formula (35). (Y １ each independently represents at least one tetravalent organic group selected from the group consisting of an aliphatic group having 2 to 20 carbon atoms, an alicyclic group having 4 to 40 carbon atoms, and an aromatic group having 6 to 40 carbon atoms. １ R each independently represents a divalent organic group having 2 to 40 carbon atoms. ６０ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having 2 to 20 carbon atoms and an ethylenically unsaturated double bond.

23. Z contained in the repeating unit represented by formula (33), the repeating unit represented by formula (34), and the repeating unit represented by formula (35) １ are each independently an organic group represented by any one of formulas (36) to (38). (X １ are each independently a direct bond or a divalent group represented by formula (39), and R ６１ each independently represents an alkyl group having 1 to 4 carbon atoms; X ２ is a divalent group represented by the formula (2) or a divalent group represented by the formula (3), each v independently represents 0 or 1, and * represents a bonding point to bond to the imide structure or amide structure. (* indicates the attachment point on the imide or amide bond side. ** indicates the attachment point on the benzene ring side.) 24. A photosensitive resin sheet in which the photosensitive resin composition according to any one of claims 1 to 5 is formed in the form of a film on a support.

25. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5.

26. A method for producing a cured product, comprising the steps of: forming the photosensitive resin composition according to any one of claims 1 to 5 into a film on a substrate; exposing the film of the photosensitive resin composition to light; developing the exposed film of the photosensitive resin composition; and curing the developed film of the photosensitive resin composition.

27. An electronic component comprising the cured product according to claim 25.

28. A display device comprising the cured product according to claim 25.

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