Positive photosensitive resin composition, insulating resin film, method for forming insulating resin film, and semiconductor device

Abstract

This positive photosensitive resin composition includes (A) an alkali-soluble resin, (B) an imide compound, (C) a photoacid generator, and (D) a thermal crosslinking agent. The alkali-soluble resin is a resin including a constituent unit that is a group resulting from removing one or more hydrogen atoms from a bisphenol imide compound represented by formula (I). The imide compound is a compound represented by formula (II). R1 is a hydroxyphenyl group that may be substituted with an alkyl group.

Description

Positive photosensitive resin composition, insulating resin film, method for forming insulating resin film, and semiconductor device

[0001] The present disclosure relates to a positive photosensitive resin composition, an insulating resin film having a pattern including openings, a method for forming an insulating resin film having a pattern including openings, and a semiconductor device.

[0002] Patent Document 1 discloses a positive photosensitive resin composition containing an alkali-soluble resin having an imide bond and a phenolic hydroxyl group as a material capable of forming a surface protective layer or an interlayer insulating layer of a semiconductor element.

[0003] International Publication No. 2021 / 261448

[0004] One aspect of the present disclosure relates to a positive photosensitive resin composition containing an alkali-soluble resin having an imide group and a phenolic hydroxyl group, and further improving the developability and the tensile strength and heat resistance of the cured film.

[0005] The present disclosure includes the following: [1] A photopolymerizable composition comprising: (A) an alkali-soluble resin; (B) an imide compound; (C) a photoacid generator that generates an acid by light; and (D) a thermal crosslinker that crosslinks the alkali-soluble resin by heat, wherein the alkali-soluble resin is represented by the following formula (I): The resin includes a structural unit which is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by the following formula (II): In formula (I), R １ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z １ is a tetravalent organic group, and two R １ may be the same or different, and in formula (II), R ２ is a monovalent organic group, and Z ２ is a tetravalent organic group, X is a divalent organic group, and n is an integer of 1 or more. [2] A positive photosensitive resin composition, ２ [3] The positive photosensitive resin composition according to [1], wherein the imide compound is a compound represented by the following formula (II'): In formula (II′), R ２ , X and n are R in formula (II) ２ , X and n are defined as ４ [4] The positive photosensitive resin composition according to [1] or [2], wherein is a divalent organic group or a covalent bond. [4] The positive photosensitive resin composition comprises: (A) an alkali-soluble resin; (C) a photoacid generator which is a compound that generates an acid by light; and (D) a thermal crosslinking agent which is a compound that crosslinks the alkali-soluble resin by heat, wherein the alkali-soluble resin is represented by the following formula (I): a first constitutional unit which is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by the following formula (III): and a second structural unit which is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by formula (I): １ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z １ is a tetravalent organic group, and two R １ may be the same or different, and in formula (III), R ３ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z ２ is a tetravalent organic group, X is a divalent organic group, n is an integer of 1 or more, and a plurality of R ３ , Z ２ and X may be the same or different from each other. [5] A positive photosensitive resin composition, wherein the bisphenolimide compound represented by formula (III) is a bisphenolimide compound represented by formula (III'): In formula (III′), R ３ , X and n are R in formula (III) ３ , X and n are defined as ４is a divalent organic group or a covalent bond. [6] The positive photosensitive resin composition according to [4] or [5], wherein the resin comprises a first component having a polymer chain containing the first structural unit, and a second component having a polymer chain containing the second structural unit and different from the first component. [7] The positive photosensitive resin composition according to any of [1] to [6], wherein X is a divalent group having an aromatic group substituted with a hydroxy group, a carboxy group, or both of them. [8] The positive photosensitive resin composition according to any of [1] to [6], wherein X is a group represented by the following formula (10): In formula (10), Z is a divalent group represented by ５ is a divalent organic group or a covalent bond, and Z ６ and Z ７ [9] The positive photosensitive resin composition according to any one of [1] to [6], wherein each of the groups independently represents a hydroxy group or a carboxy group. In formula (I′), R １ is R in formula (I) １ is defined similarly to Z ３is a divalent organic group or a covalent bond.

[10] The positive photosensitive resin composition according to any one of [1] to [9], wherein the resin is a novolak resin further containing a structural unit derived from a reactive compound selected from an aldehyde compound, a compound having multiple methoxymethyl groups, and a compound having multiple hydroxymethyl groups.

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

[10] , wherein the thermal crosslinking agent contains an alkoxy compound having multiple alkoxy groups.

[12] A method for forming an insulating resin film, comprising: exposing a portion of a photosensitive layer containing the positive photosensitive resin composition according to any one of [1] to

[11] ; forming an insulating resin film having a pattern including openings by development that removes portions of the photosensitive layer; and heating the insulating resin film.

[13] An insulating resin film having a pattern including openings, comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[11] .

[14] A semiconductor device comprising: a semiconductor chip; and a wiring section including a conductor wiring layer connected to the semiconductor chip and one or more insulating layers, wherein at least a part of the one or more insulating layers is the insulating resin film according to

[13] .

[0006] With regard to a positive-type photosensitive resin composition containing an alkali-soluble resin having an imide group and a phenolic hydroxyl group, the developability and the tensile strength and heat resistance of the cured film can be further improved.

[0007] 1 is a flowchart showing an example of a method for forming an insulating resin film having a pattern.

[0008] The present invention is not limited to the following examples. In this disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended function of the process is achieved. The term "layer" encompasses not only a structure that is formed over the entire surface when observed in a plan view, but also a structure that is formed only on a portion of the surface. Numerical ranges indicated using "to" indicate ranges that include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range of a certain stage may be replaced with the upper or lower limit of a numerical range of another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with the value shown in the examples.

[0009] Photosensitive Resin Composition An example of a photosensitive resin composition includes an alkali-soluble resin, a photoacid generator that generates an acid when exposed to light, and a thermal crosslinker that crosslinks the alkali-soluble resin when exposed to heat. The photosensitive resin composition may further include a solvent. The photosensitive resin composition according to the present disclosure can function as a positive-type photosensitive resin composition based on a change in solubility in an alkaline developer due to exposure to light. Furthermore, a film including the photosensitive resin composition according to the present disclosure can be thermally cured mainly through a crosslinking reaction between the thermal crosslinker and the alkali-soluble resin to form an insulating resin film that is a cured film including a cured product of the photosensitive resin composition.

[0010] (A) Alkali-soluble resin and (B) imide compound The alkali-soluble resin is a compound represented by the following formula (I): In other words, the resin may have a polymer chain containing a structural unit derived from a bisphenolimide compound represented by formula (I). １ is a hydroxyphenyl group optionally substituted with an alkyl group (e.g., an alkyl group having 1 to 3 carbon atoms), and Z １ is a tetravalent organic group, and two R １ may be the same or different from each other.

[0011] The photosensitive resin composition contains, as a component other than the alkali-soluble resin containing a constituent unit derived from a bisphenolimide compound represented by formula (I), a compound represented by formula (II): In formula (II), R ２ is a monovalent organic group, and Z ２ is a tetravalent organic group, X is a divalent organic group, and n is an integer of 1 or more.

[0012] The alkali-soluble resin contains a structural unit derived from a bisphenolimide compound represented by formula (I) as a first structural unit, and also contains a structural unit derived from a bisphenolimide compound represented by formula (III): In formula (III), R ３ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z ２ is a tetravalent organic group, X is a divalent organic group, n is an integer of 1 or more, and a plurality of R ３ , Z ２ and X may be the same or different. The photosensitive resin composition may contain, as the alkali-soluble resin, a first component having a polymer chain containing the first structural unit, and a second component having a polymer chain containing the second structural unit and different from the first component. The photosensitive resin composition may contain, as the alkali-soluble resin, a resin having a polymer chain containing both the first structural unit and the second structural unit. The photosensitive resin composition may contain an alkali-soluble resin that is a resin having a polymer chain containing the second structural unit, and an imide compound represented by formula (II). The photosensitive resin composition may further contain an alkali-soluble resin that does not contain a structural unit (first structural unit) that is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by formula (I).

[0013] R in formula (I) １ Examples of the group include monovalent groups represented by the following formula (20) or (21): ２０is an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms). In formula (20), the number of hydrogen atoms at the ortho or para positions relative to the phenolic hydroxyl group (—OH) may be 1 or more and 3 or less.

[0014] R １ may be a group represented by the following formula (201), (202), (203) or (204). ２０ is R in formula (20) ２０ The alkali-soluble resin is particularly defined as R １ may have a structural unit derived from a bisphenolimide compound represented by the formula (204).

[0015] Z in formula (I) １ may be a group having one cyclic hydrocarbon group which may have a substituent, or two or more cyclic hydrocarbon groups which may have a substituent and a divalent organic group or covalent bond which bonds them. １ Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxy group, a carboxy group, and an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms).

[0016] Z １ Examples of the cyclic hydrocarbon group that can constitute the above group include groups in which one or more hydrogen atoms have been removed from the following cyclic hydrocarbon compounds:

[0017] Z １ The divalent organic group linking the two cyclic hydrocarbon groups may be, for example, a divalent group selected from an oxy group (-O-), a thio group (-S-), a carbonyl group, an alkylene group having 1 to 3 carbon atoms, a phenylene group, an alkylphenylene group, and groups consisting of combinations thereof. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an ethylidene group, a propane-1,3-diyl group, a propane-1,1-diyl group, and a propane-2,2-diyl group. Z １ Specific examples of the divalent organic group linking two cyclic hydrocarbon groups include alkylene groups having 1 to 3 carbon atoms as well as the following:

[0018] In these formulas, R１０ represents an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group), and multiple R １０ may be the same or different. q represents an integer of 0 to 4, and multiple q's in one formula may be the same or different. R １１ represents an alkylene group (e.g., propane-2,2-diyl group, methylene group), an oxy group, a thio group, or a direct bond. １２ represents an alkylene group (for example, an ethane-1,2-diyl group).

[0019] The bisphenolimide compound represented by formula (I) is a compound represented by the following formula (I') or (I''): The compound represented by R in formula (I′) and (I″) may be １ is R in formula (I) １ Z in formula (I') is defined as ３ is a divalent organic group or a covalent bond. ３ Examples of divalent organic groups as １ The formula (I') may be, for example, the following formula (IA) or (IB). R in formulas (IA) and (IB) １ and Z ３ is R in formula (I'). １ and Z ３ The structural unit derived from the bisphenolimide compound of formula (IB) can contribute to improving the mechanical strength of the cured film and reducing the linear expansion coefficient.

[0020] The resin containing a structural unit derived from a bisphenolimide compound represented by formula (I) may be a novolac resin. The novolac resin has a polymer chain containing, for example, a structural unit (first structural unit) derived from the bisphenolimide compound represented by formula (I) and a structural unit (hereinafter sometimes referred to as an "additional unit") derived from a reactive compound selected from an aldehyde compound, a compound having multiple methoxymethyl groups, and a compound having multiple hydroxymethyl groups. In the polymer chain of the novolac resin, the first structural unit and the additional unit may be bonded alternately. The structural unit derived from the bisphenolimide compound may be a residue of a bisphenolimide compound in which one or more hydrogen atoms have been removed from a benzene ring to which a phenolic hydroxyl group is bonded. The structural unit derived from the bisphenolimide compound may be bonded to another structural unit at the ortho or para position relative to the phenolic hydroxyl group. The polymer chain of the novolac resin may further contain a structural unit derived from a phenolic compound selected from phenol, o-cresol, m-cresol, and p-cresol.

[0021] The aldehyde compound constituting the novolac resin may be formaldehyde. The compound having multiple methoxymethyl groups may be a compound having an aromatic ring (e.g., a benzene ring) to which methoxymethyl groups are bonded. The compound having multiple hydroxymethyl groups may be a compound having an aromatic ring (e.g., a benzene ring) to which hydroxymethyl groups are bonded. Examples of compounds having multiple methoxymethyl groups include compounds represented by the following formula (22) or (23). In these formulas, R １０ represents an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group). １０ may be the same or different. p represents an integer of 0 to 4, and q and r each independently represent an integer of 0 to 4. The compound having multiple methoxymethyl groups may be bis(methoxymethyl)biphenyl, dimethoxymethylbenzene, or a combination thereof. An example of a compound having multiple hydroxymethyl groups includes 2,6-bis(hydroxymethyl)-p-cresol.

[0022] The residue derived from formaldehyde is usually a methylene group. The residue derived from a compound having two or more methoxymethyl groups can be, for example, a divalent group represented by the following formula (22A) or (23B). R in formula (22A) and (23B) １０ , p, q and r are R in formulas (22) and (23). １０ , p, q and r are defined similarly.

[0023] The following formula is an example of a partial structure of a polymer chain that can be possessed by a novolak resin containing a structural unit (first structural unit) derived from a bisphenolimide compound and a structural unit (additional unit) derived from a reactive compound. The polymer chain in this example is represented by formula (I'), and R ２ is a group represented by formula (204), and a structural unit derived from a compound having a plurality of methoxymethyl groups represented by formula (22).

[0024] Novolac resins having polymer chains containing structural units derived from bisphenolimide compounds can be synthesized, for example, by methods similar to those used to synthesize general phenol novolac resins or cresol novolac resins. Novolac resins can be produced by an addition-condensation reaction, in the presence of an acid catalyst, between a phenolic compound component containing a bisphenolimide compound represented by formula (I) and a reactive compound selected from an aldehyde compound, a compound having multiple methoxymethyl groups, and a compound having multiple hydroxymethyl groups. The phenolic compound component may further contain a phenolic compound selected from phenol, o-cresol, m-cresol, and p-cresol. The proportion of the bisphenolimide compound in the phenolic compound component may be 10 mol% to 100 mol%, 20 mol% to 100 mol%, 30 mol% to 100 mol%, or 40 mol% to 100 mol%, based on the total amount of the phenolic compound component. A high proportion of the bisphenolimide compound tends to provide particularly excellent effects in terms of a good shape and high resolution of the insulating resin film. From the same viewpoint, the proportion of the bisphenolimide compound may be 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, or 90 mol% or more, based on the total amount of the phenol compound components, or may be substantially 100 mol%.

[0025] The phenol compound component used in producing the alkali-soluble novolak resin may further contain a bisphenolimide compound represented by formula (III). In this case, a novolak resin having a polymer chain containing a first structural unit derived from the bisphenolimide compound represented by formula (I) and a second structural unit derived from the bisphenolimide compound represented by formula (III) may be produced. The alkali-soluble resin may contain a combination of a novolak resin (first component) having a polymer chain containing the first structural unit and a novolak resin (second component) having a polymer chain containing the second structural unit but not the first structural unit.

[0026] R in formula (III) ３ Examples of the formula (I) include R １ The examples are the same as those of the formula (III). ２Examples of the group are Z in formula (I) １ Examples of X in formula (III) are the same as the examples of X in formula (II) described below. The weight-average molecular weight of the bisphenolimide compound represented by formula (III) may be the same as the weight-average molecular weight of the imide compound represented by formula (II) described below.

[0027] The bisphenolimide compound represented by formula (III) may be a compound represented by the following formula (III'): ３ , X and n are R in formula (III) ３ , X and n are defined as ４ is a divalent organic group or a covalent bond. ４ Examples of the formula (I') include Z ３ This is similar to the example above.

[0028] When the alkali-soluble resin is one or more resins (e.g., novolak resins) having a polymer chain containing first and second structural units, the proportion of the second structural units relative to the total amount of the first and second structural units may be 1% by mass or more and 90% by mass or less. The proportion of the second structural units relative to the total amount of the first and second structural units may be 3% by mass or more, or 5% by mass or more, or 85% by mass or less, 80% by mass or less, 75% by mass or less, 60% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less.

[0029] The weight average molecular weight (Mw) of the alkali-soluble resin may be 1,000 to 500,000, 2,000 to 400,000, 3,000 to 350,000, or 5,000 to 300,000, from the viewpoint of the balance between solubility in an alkaline aqueous solution, photosensitive properties, and mechanical strength of the insulating resin film. In the present disclosure, the weight average molecular weight is a converted value measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

[0030] The photosensitive resin composition may contain an imide compound represented by the above formula (II).２ Examples of the group are Z in formula (I) １ This is similar to the example above.

[0031] R in formula (II) ２ may be a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include an aromatic hydrocarbon group (e.g., a phenyl group), an alkyl group, an alkenyl group, and an alkynyl group. Examples of the substituent which the aromatic hydrocarbon group may have include an alkyl group (e.g., an alkyl group having 1 to 3 carbon atoms), a hydroxy group, and a carboxy group. R ２ may be a hydroxyphenyl group optionally substituted with an alkyl group, in which case R ２ Examples of the formula (I) include R １ The examples include groups similar to those shown above.

[0032] X in formula (II) may be one cyclic hydrocarbon group which may have a substituent, or a divalent group having two or more cyclic hydrocarbon groups which may have a substituent and a divalent organic group or covalent bond which bonds them. Examples of the cyclic hydrocarbon group in X include groups in which one or more hydrogen atoms have been removed from the following cyclic hydrocarbon compounds. Examples of the divalent organic group which bonds two cyclic hydrocarbon groups in X include Z １ The divalent organic group linking two cyclic hydrocarbon groups in X includes the same groups as those mentioned above as examples of the divalent organic group linking two cyclic hydrocarbon groups in X. Examples of the substituent that the cyclic hydrocarbon group in X may have include a hydroxy group, a carboxy group, and an alkyl group (e.g., an alkyl group having 1 to 3 carbon atoms). The cyclic hydrocarbon group in X may also be an aromatic group (e.g., a phenylene group) substituted with a hydroxy group, a carboxy group, or both.

[0033] X is represented by the following formula (10): In formula (10), Z may be a divalent group represented by the following formula: ５ is a divalent organic group or a covalent bond, and Z ６ and Z ７ are each independently a hydroxy group or a carboxy group. ５ Examples of the formula (I) include Z １The divalent organic group bonding two cyclic hydrocarbon groups includes the same groups as those mentioned above. X may be a group represented by the following formula (10a) or (10b). Z in formula (10a) and (10b) ５ , Z ６ and Z ７ is Z in formula (10) ５ , Z ６ and Z ７ is defined similarly.

[0034] The imide compound is represented by the following formula (II'): In formula (II′), R ２ , X and n are R in formula (II) ２ , X and n are defined similarly. Z ４ is a divalent organic group or a covalent bond. ４ Examples of the formula (I') include Z ３ This is similar to the example above.

[0035] The weight average molecular weight of the imide compound represented by formula (II) may be, for example, 5,000 or more and 50,000 or less. The weight average molecular weight of the imide compound represented by formula (II) may be 10,000 or more, or 40,000 or less, 35,000 or less, or 30,000 or less.

[0036] The imide compound represented by formula (II) can be synthesized, for example, by reacting an acid anhydride compound represented by the following formula (a), an amine compound represented by the following formula (b), and an amine compound represented by the following formula (c).

[0037] When the photosensitive resin composition contains the imide compound represented by formula (II), the content thereof may be 1% by mass or more and 90% by mass or less, based on the total amount of the alkali-soluble resin (or the resin having a structural unit derived from the bisimide phenol compound represented by formula (I)) and the imide compound represented by formula (II). The content of the imide compound represented by formula (II) may be 3% by mass or more, or 5% by mass or more, based on the total amount of the alkali-soluble resin (or the resin having a structural unit derived from the bisimide phenol compound represented by formula (I)) and the imide compound represented by formula (II), and may be 85% by mass or less, 80% by mass or less, 75% by mass or less, 60% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less.

[0038] In the photosensitive resin composition, the total ratio of the alkali-soluble resin (or the resin having a structural unit derived from the bisimide phenol compound represented by formula (I)) and the imide compound represented by formula (II) may be 50% by mass or more and 99% by mass or less, 60% by mass or more and 99% by mass or less, or 70% by mass or more and 99% by mass or less, based on the amount of components other than the solvent in the photosensitive resin composition.

[0039] (C) Photoacid Generator The photoacid generator (C) contains one or more compounds that generate an acid upon exposure to light (e.g., ultraviolet light) and functions as a photosensitizer in the photosensitive resin composition. The action of the acid generated by the photoacid generator upon absorption of light selectively increases the solubility in an alkaline aqueous solution of the portion of the photosensitive layer that has been irradiated with light.

[0040] The compound constituting the photoacid generator may be selected from compounds generally used as photoacid generators. The compound that generates an acid when exposed to light may be, for example, an o-quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, or a triarylsulfonium salt, or a combination of two or more selected from these.

[0041] In order to improve the sensitivity of exposure, the photoacid generator may contain an o-quinone diazide compound. The o-quinone diazide compound contains an aromatic group, an oxo group (=O), and a diazide group (=N). ＋ = N － ) in which an oxo group and a diazido group are bonded to adjacent carbon atoms in an aromatic group. The aromatic group may be, for example, a group obtained by removing a hydrogen atom from naphthalene or benzene.

[0042] The o-quinonediazide compound may have, as a group containing an oxo group and a diazide group, for example, a group represented by the following formula (3a), (3b) or (3c).

[0043] The compound having a group represented by formula (3a), (3b), or (3c) may be, for example, a product of a condensation reaction between o-quinone diazide sulfonyl chloride and a hydroxy compound and / or an amino compound in the presence of a dehydrochlorinating agent. In this case, the o-quinone diazide compound may be a compound having a residue derived from a hydroxy compound or an amino compound and a group represented by formula (3a), (3b), or (3c). For example, a compound having a group represented by formula (3a) can be obtained from naphthoquinone-1,2-diazide-5-sulfonyl chloride. A compound having a group represented by formula (3b) can be obtained from naphthoquinone-1,2-diazide-6-sulfonyl chloride. A compound having a group represented by formula (3c) can be obtained from benzoquinone-1,2-diazide-4-sulfonyl chloride.

[0044] Hydroxy compounds that can be used to synthesize o-quinone diazide compounds are compounds having one or more hydroxyl groups. The residue of a hydroxy compound can be a group obtained by removing one or more hydrogen atoms from the hydroxyl group of a hydroxy compound. Examples of hydroxy compounds include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. phenone, 2,3,4,2',3'-pentahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)propane, 4b,5,9b,10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno[2,1-a]indene, tris(4-hydroxyphenyl)methane, and tris(4-hydroxyphenyl)ethane.

[0045] Specific examples of the compound having a residue of a hydroxy compound and a group represented by formula (3a), (3b), or (3c) include compounds represented by the following formulas (31), (32), (33), (34), (35), or (36). These compounds tend to absorb light in an appropriate wavelength range for exposure of the photosensitive layer.

[0046] In formulas (31) to (36), Q represents a group represented by formula (3a), (3b), or (3c), or a hydrogen atom, and multiple Qs in the same molecule may be the same or different, and at least one of the multiple Qs in the same molecule is a group represented by formula (3a), (3b), or (3c). ３０ represents an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group), and multiple R３０ may be the same or different. ３１ represents an alkanetriyl group having 1 to 3 carbon atoms (for example, a methanetriyl group or an ethane-1,1,1-triyl group), and each of the multiple p's independently represents an integer of 0 to 4. In formula (32), each of the multiple q's independently represents an integer of 0 to 4. In formula (33), each of the multiple r's independently represents an integer of 0 to 4, and each of the multiple s's independently represents an integer of 0 to 3. In formula (34), each of the multiple t's independently represents an integer of 0 to 4. In formula (35), each of the multiple u's independently represents an integer of 0 to 4, and each of the multiple v's independently represents an integer of 0 to 3. In formula (36), w represents an integer of 0 to 4, and x represents an integer of 0 to 2.

[0047] The amino compound that can be used to synthesize the o-quinonediazide compound is a compound having one or more amino groups. The residue of the amino compound can be a group in which one or more hydrogen atoms have been removed from the amino group of the amino compound. Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and bis(4-amino-3-hydroxyphenyl)hexafluoropropane.

[0048] From the viewpoint of good sensitivity, the content of the photoacid generator may be 1 to 50% by mass, 3 to 35% by mass, or 5 to 20% by mass relative to the total content of the alkali-soluble resin as component (A) and the imide compound as component (B).

[0049] (D) Thermal Crosslinking Agent The thermal crosslinking agent of component (D) contains one or more compounds that crosslink the alkali-soluble resin by heat. The compound constituting the thermal crosslinking agent may have multiple functional groups that can react with the alkali-soluble resin and bond to the polymer chain of the alkali-soluble resin. Examples of such functional groups include alkoxy groups, epoxy groups, and oxazoline groups. The thermal crosslinking agent may contain an alkoxy compound having multiple alkoxy groups.

[0050] The alkoxy compound that can be used as a thermal crosslinking agent is thought to function as a thermal crosslinking agent that crosslinks the polymer chains of the alkali-soluble resin mainly through a reaction between an aromatic group (phenylene group) to which a phenolic hydroxyl group is bonded and an alkoxy group. The number of alkoxy groups in the alkoxy compound may be 2 or more, 3 or more, or 4 or more, and may be 20 or less, 15 or less, or 10 or less.

[0051] At least a portion of the two or more alkoxy groups of the alkoxy compound may be methoxy groups. In other words, the alkoxy compound may have multiple methoxy groups. The alkoxy compound may have four or more methoxy groups.

[0052] The alkoxy compound may have a cyclic group obtained by removing one or more hydrogen atoms from benzene, 1,3,5-triazine, glycoluril, 2-imidazolidinone, or urea, and an alkoxyalkyl group (e.g., a methoxymethyl group or a 1,3-dimethoxypropan-2-yl group) may be bonded to the cyclic group. An alkoxy compound having a cyclic group (benzene ring) obtained by removing a hydrogen atom from benzene may have a phenolic hydroxyl group bonded to the cyclic group. In the present disclosure, a compound having an alkoxy group and a phenolic hydroxyl group can be considered a thermal crosslinking agent for component (D) rather than an alkali-soluble resin. An alkoxy compound having an alkoxy group and a phenolic hydroxyl group can contribute to improving the sensitivity of the photosensitive resin composition.

[0053] The weight average molecular weight of the alkoxy compound may be 3000 or less, 2000 or less, or 1500 or less, or may be 100 or more, from the viewpoint of the balance of solubility in an alkaline developer, photosensitive properties, and mechanical strength.

[0054] Specific examples of alkoxy compounds having a phenolic hydroxyl group include compounds represented by the following formula (41), (42), (43), (44), (45), or (46). Specific examples of alkoxy compounds having a cyclic group formed by removing one or more hydrogen atoms from 1,3,5-triazine, glycoluril, 2-imidazolidinone, or urea include compounds represented by the following formula (47), (48), (49), or (50).

[0055] In formulas (41) to (50), R ４０ represents an alkoxyalkyl group, and multiple R ４０ may be the same or different. ４０ may be a methoxyalkyl group or a dimethoxyalkyl group, an example of which is a methoxymethyl group (-CH ２ OCH ３ ), and a 1,3-dimethoxypropan-2-yl group represented by the following formula:

[0056] From the viewpoints of heat resistance of the insulating resin film (cured film) and suppression of warpage, the content of the thermal crosslinking agent (or alkoxy compound) may be 1 to 70 mass %, 2 to 50 mass %, or 3 to 40 mass % relative to the total content of the alkali-soluble resin of component (A) and the imide compound of component (B).

[0057] In the photosensitive resin composition, the total content of the (A) alkali-soluble resin, (B) imide compound, (C) photoacid generator, and (D) thermal crosslinking agent may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, based on the amount of the photosensitive resin composition. When the photosensitive resin composition contains a solvent, the amount of the photosensitive resin composition herein is the amount excluding the solvent.

[0058] Other Components In addition to the components exemplified above, the photosensitive resin composition may further contain other components such as an acrylic elastomer, an adhesion aid, a solvent, a compound that generates an acid upon heating, a dissolution promoter, a dissolution inhibitor, a Cu rust inhibitor, a coupling agent, a surfactant, and a leveling agent. The photosensitive resin composition may further contain, in addition to component (A), an alkali-soluble resin that does not fall under component (A).

[0059] An acrylic elastomer is a polymer containing one or more (meth)acrylic acid esters as monomer units. The (meth)acrylic acid esters may be (meth)acrylic acid alkyl esters having an alkyl group which may have a substituent. "(Meth)acrylic" refers to both acrylic and methacrylic.

[0060] The acrylic elastomer comprises one or more monomer units having a polyoxyalkylene group. The polyoxyalkylene group has the formula: -(OR ５１ ) ｎ -, and R ５１ represents an alkylene group, and n represents an integer of 2 or more. ５１ may be an alkylene group having 2 to 5 carbon atoms. The number of repetitions n of the oxyalkylene group may be 10 or less, 5 or less, or 3 or less. Examples of polyoxyalkylene groups include polyoxyethylene groups (-(OCH ２ CH ２ ) ｎ -), and polypropylene groups (-(OCH(CH ３ ) CH ２ ) ｎ The monomer unit having a polyoxyalkylene group may be a group that does not have a hydroxyl group, a carboxy group, or an amino group.

[0061] The monomer unit having a polyoxyalkylene group may be a monomer unit derived from a (meth)acrylic acid ester having a polyoxyalkylene group, and examples thereof include those represented by the following formula (51). In formula (51), R ５０ represents a hydrogen atom or a methyl group, and R ５１ represents an alkylene group, and R ５２represents a hydrocarbon group, and n represents an integer of 2 or more. ５１ Examples of R are as described above. ５２ may be an unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group) or an aryl group (eg, phenyl group).

[0062] The acrylic elastomer may further contain a monomer unit other than the monomer unit having a polyoxyalkylene group. The proportion of the monomer units having a polyoxyalkylene group in the acrylic elastomer may be 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, or 70 mol% or more, based on all the monomer units contained in the acrylic elastomer, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. When the proportion of the monomer units having a polyoxyalkylene group is within these ranges, particularly significant effects are likely to be obtained in terms of reduced cloudiness of the photosensitive layer and high mechanical strength and large elongation of the insulating resin film.

[0063] The acrylic elastomer may further contain a monomer unit having a hydroxyl group. The monomer unit having a hydroxyl group may be a group that does not have a polyoxyalkylene group, a carboxy group, or an amino group. The monomer unit having a hydroxyl group may be a monomer unit derived from a (meth)acrylic acid ester having a hydroxyalkyl group or a (meth)acrylamide having a hydroxyalkyl group, examples of which include those represented by the following formula (52): In formula (52), R ５０ represents a hydrogen atom or a methyl group, and Z ２ is —O— or —NH—, and R ５３ represents an alkylene group. ５３ may be an alkylene group having 1 to 20, 1 to 10, or 1 to 4 carbon atoms, examples of which include an ethane-1,2-diyl group and a butane-1,4-diyl group. The proportion of monomer units having a hydroxyl group in the acrylic elastomer may be 1 mol % or more, 2 mol % or more, or 3 mol % or more, and may be 20 mol % or less, 15 mol % or less, or 10 mol % or less, based on all monomer units contained in the acrylic elastomer.

[0064] The acrylic elastomer may further contain a monomer unit having a carboxy group. The monomer unit having a carboxy group may be a group that does not have a polyoxyalkylene group, a hydroxyl group, or an amino group. The monomer unit having a carboxy group may be a monomer unit derived from a (meth)acrylic acid ester having a carboxy group, examples of which include those represented by the following formula (53A) or (53B). In formulas (53A) and (53B), R ５０ represents a hydrogen atom or a methyl group. ５４ represents an alkylene group. ５４ may be an alkylene group having 1 to 20, 1 to 10, or 1 to 4 carbon atoms, examples of which include an ethane-1,2-diyl group. The proportion of monomer units having a carboxy group in the acrylic elastomer may be 3 mol % or more, 5 mol % or more, or 10 mol % or more, and may be 30 mol % or less, 25 mol % or less, or 20 mol % or less, based on all monomer units contained in the acrylic elastomer.

[0065] The acrylic elastomer may further contain a monomer unit having an amino group. The monomer unit having an amino group may be a group that does not have a polyoxyalkylene group, a hydroxyl group, or a carboxyl group. The monomer unit having an amino group may be a monomer unit derived from a (meth)acrylic acid ester having a secondary or tertiary amino group, examples of which include those represented by the following formula (54): In formula (54), R ５０ represents a hydrogen atom or a methyl group, and R ５５ represents a hydrogen atom or an alkyl group, and R ５６ , R ５７ , R ５８ and R ５９ R each independently represents an alkyl group. ５５ may be an alkyl group having 1 to 20, 1 to 10, or 1 to 5 carbon atoms (e.g., a methyl group). ５６ , R ５７ , R ５８ and R ５９may be an alkyl group (e.g., a methyl group) having 1 to 20, 1 to 10, or 1 to 5 carbon atoms. The proportion of the monomer units having an amino group in the acrylic elastomer may be 1 mol % or more, 2 mol % or more, or 3 mol % or more, and may be 20 mol % or less, 15 mol % or less, or 10 mol % or less, based on all the monomer units contained in the acrylic elastomer.

[0066] The acrylic elastomer may further contain a monomer unit having an unsubstituted alkyl group. The monomer unit having an unsubstituted alkyl group may be a monomer unit derived from a (meth)acrylic acid ester having an unsubstituted alkyl group, and examples thereof include those represented by the following formula (55): In formula (55), R ５０ represents a hydrogen atom or a methyl group, and R ６０ represents an unsubstituted alkyl group having 4 to 20 carbon atoms. ６０ Examples include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (or lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups.

[0067] The acrylic elastomer may be a copolymer containing a monomer unit having a polyoxyalkylene group but not having a hydroxyl group, a carboxy group, or an amino group, a monomer unit having a hydroxyl group but not having a polyoxyalkylene group, a carboxy group, or an amino group, a monomer unit having a carboxy group but not having a polyoxyalkylene group, a hydroxyl group, or an amino group, and a monomer unit having an amino group but not having a polyoxyalkylene group, a hydroxyl group, or a carboxy group. The acrylic elastomer may be a copolymer consisting only of a monomer unit having a polyoxyalkylene group, a monomer unit having a hydroxyl group, a monomer unit having a carboxy group, and a monomer unit having an amino group, or a copolymer consisting only of these monomer units and the remaining monomer units having an unsubstituted alkyl group.

[0068] The content of the acrylic elastomer may be 0.5% by mass or more and 50% by mass or less relative to the content of the alkali-soluble resin. The content of the acrylic elastomer may be 1% by mass or more, or 2% by mass or more, or 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less relative to the content of the alkali-soluble resin.

[0069] The photosensitive resin composition may further contain other elastomers in addition to the acrylic elastomers exemplified above. The other elastomers include acrylic elastomers, styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, and silicone elastomers, which are polymers that do not contain a monomer unit having a polyoxyalkylene group. The content of the other elastomers may be 0% by mass or more and 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, based on the content of the alkali-soluble resin.

[0070] The adhesion promoter may include a nitrogen-containing aromatic compound, examples of which include 1H-tetrazole, 5-aminotetrazole, 5-phenyltetrazole, and 5-methyltetrazole. The content of the adhesion promoter may be 0 to 20 mass%, 0.01 to 20 mass%, 0.015 to 10 mass%, or 0.02 to 7 mass% relative to the content of the alkali-soluble resin of component (A).

[0071] Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more. The solvent may include ethyl lactate, γ-butyrolactone, or a combination thereof. In a photosensitive resin composition containing a solvent, the concentration of components other than the solvent (solid content) may be 1 to 80% by mass based on the mass of the photosensitive resin composition containing the solvent.

[0072] The compound that generates an acid upon heating promotes the thermal crosslinking reaction between the alkali-soluble resin and the oxazoline compound or alkoxy compound, which can result in further improved heat resistance of the cured film. The compound that generates an acid upon heating can also contribute to improved resolution. Examples of the compound that generates an acid upon heating include salts formed from a strong acid and a base, such as onium salts, and imide sulfonates. The content of the compound that generates an acid upon heating may be 0 to 30% by mass, 0.1 to 30% by mass, 0.2 to 20% by mass, or 0.5 to 10% by mass relative to the content of the alkali-soluble resin of component (A).

[0073] The dissolution promoter is a component that increases the dissolution rate of the exposed area in a developer, and can contribute to improving sensitivity and resolution. The dissolution promoter may include a compound having a carboxy group, a sulfo group, or a sulfonamide group. The content of the dissolution promoter may be 0 to 30% by mass, or 0.01 to 30% by mass, relative to the content of the alkali-soluble resin of component (A).

[0074] The dissolution inhibitor is a compound that inhibits the dissolution of exposed areas in an alkaline aqueous solution and is used to control the film thickness, development time, and contrast after development. Examples of dissolution inhibitors include diphenyliodonium nitrate, bis(p-tert-butylphenyl)iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. The content of the dissolution inhibitor may be 0 to 20% by mass, 0.01 to 20% by mass, 0.01 to 15% by mass, or 0.05 to 10% by mass relative to the content of the alkali-soluble resin of component (A).

[0075] The coupling agent may include an organic silane compound (silane coupling agent), an aluminum chelate compound, or a combination thereof. Examples of commercially available organic silane compounds include KBM-403, KBM-803, and KBM-903 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). The content of the coupling agent may be 0 to 20% by mass, 0.1 to 20% by mass, or 0.5 to 10% by mass relative to the content of the alkali-soluble resin of component (A).

[0076] Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Examples of commercially available products include Megafac F-171, F-565, and RS-78 (trade names, manufactured by DIC Corporation). The content of the surfactant or leveling agent may be 0 to 5 mass%, 0.001 to 5 mass%, or 0.01 to 3 mass%, relative to the content of the alkali-soluble resin of component (A).

[0077]

[0023] Method for forming an insulating resin film having a pattern including openings can be formed by photolithography using the photosensitive resin composition according to the present disclosure. Fig. 1 is a flowchart showing an example of a method for forming an insulating resin film having a pattern including openings. The method shown in Fig. 1 includes a step S1 of forming a photosensitive layer including the photosensitive resin composition, a step S2 of exposing a portion of the photosensitive layer to light, a step S3 of removing a portion of the photosensitive layer through development to form an insulating resin film having a pattern including openings, and a step S4 of heating the insulating resin film.

[0078] The photosensitive layer containing the photosensitive resin composition can be applied to, for example, a glass substrate, a semiconductor substrate, a metal oxide insulating substrate (e.g., TiO ２ , SiO ２ The photosensitive layer may be formed on any substrate, such as a silicon nitride substrate. The photosensitive layer may be formed, for example, by a method including coating a photosensitive resin composition containing a solvent on the substrate and removing the solvent from the coating. The coating may be heated to remove the solvent. The thickness of the photosensitive layer may be 0.1 to 40 μm.

[0079] A portion of the photosensitive layer is exposed by irradiation with actinic rays through a mask. The actinic rays may be ultraviolet light, visible light, or radioactive rays, and may be g-rays, h-rays, i-rays, or a combination thereof.

[0080] By developing to remove a portion of the photosensitive layer, a resin film (insulating resin film) having a pattern including openings is formed. A developer may be used for the development. Examples of development using a developer include shower development, spray development, immersion development, and puddle development. The resin film (insulating resin film) after development may be washed with water or the like.

[0081] The developer may be an alkaline aqueous solution. The alkaline aqueous solution may contain one or more bases selected from sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH). The concentration of the base in the alkaline aqueous solution may be 0.1 to 10% by mass based on the mass of the alkaline aqueous solution. The developer may contain alcohol or a surfactant.

[0082] A portion of a 5 μm-thick photosensitive layer containing a photosensitive resin composition, corresponding to a 5 μm-wide through-hole, was exposed to light, and the exposed photosensitive layer was then exposed to light at 100 mJ / m ２ When the photosensitive layer is developed under conditions in which through-holes are formed using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38 mass % at an exposure dose of 1000 nm, the remaining film thickness of the photosensitive layer may be 95% or more of the film thickness of the photosensitive layer before exposure.

[0083] By heating the resin film (insulating resin film) that is the photosensitive layer remaining after development, an insulating resin film that is a cured film containing a thermoset product of the photosensitive resin composition is formed mainly by a reaction between the alkali-soluble resin and the thermal crosslinking agent. The heating temperature may be 300°C or less, 270°C or less, or 250°C or less, or may be 160°C or more. The heating time may be, for example, 0.5 hours or more and 5 hours or less.

[0084] The resin film (insulating resin film) can be heated using a heating device such as a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, a microwave curing device, a frequency-variable microwave curing device, etc. The heating atmosphere may be, for example, an air atmosphere or an inert gas atmosphere containing nitrogen or the like.

[0085] The insulating resin film may be, for example, an insulating layer constituting a wiring portion of a semiconductor device. The semiconductor device may have a semiconductor chip, a conductor wiring layer connected to the semiconductor chip, and a wiring portion (rewiring portion) including one or more insulating layers, and at least a portion of the one or more wiring layers may be an insulating resin film including a cured product of the photosensitive resin composition according to the present disclosure.

[0086] FIG. 2 is a partial cross-sectional view showing an example of a semiconductor device having an insulating layer. The semiconductor device 100 shown in FIG. 2 includes a semiconductor chip 10 and a wiring section 20 provided on the semiconductor chip 10. The wiring section 20 includes a conductor wiring layer 31 connected to the semiconductor chip 10, a surface protective layer 41, a cover coat layer 42, and conductive balls 50. The semiconductor device 100 may be a semiconductor package having a wafer-level package (WLP) configuration. The surface protective layer 41 and the cover coat layer 42 are stacked in this order from the semiconductor chip 10 side, and the conductive balls 50 are provided outside the cover coat layer 42. The surface protective layer 41 and the cover coat layer 42 are insulating layers, and one or both of them may be an insulating resin film containing a cured product of the photosensitive resin composition according to the present disclosure.

[0087] The semiconductor chip 10 has a chip main body 11 having a circuit surface, pads 12 provided on the circuit surface of the chip main body 11, and a protective film 13 having a pattern including openings through which the pads 12 are exposed. The conductor wiring layer 31 of the wiring section 20 is a rewiring layer connected to the pads 12 and extends to the inside of the conductive balls 50 between a surface protective layer 41 and a cover coat layer 42. A connection section 32 for connecting to the conductive balls 50 is provided on an end of the conductor wiring layer 31. A barrier metal 33 is provided between the connection section 32 and the conductive balls 50. The pads 12, conductor wiring layer 31, connection section 32, barrier metal 33, and conductive balls 50 are electrically connected in this order.

[0088] The wiring portion (rewiring portion) of the semiconductor device may have multiple conductor wiring layers, and an insulating resin film containing a cured product of the photosensitive resin composition according to the present disclosure may be provided as an interlayer insulating layer provided between adjacent conductor wiring layers. In the semiconductor device, the interlayer insulating layer, the surface protective layer, or both of them may be an insulating resin film containing a cured product of the photosensitive resin composition according to the present disclosure.

[0089] The semiconductor device may be a memory. Examples of electronic devices including the semiconductor device according to the present disclosure include mobile phones, smartphones, tablet terminals, personal computers, and hard disk drives.

[0090] [Examples] The present invention is not limited to the following examples.

[0091] 1. Raw materials (A) Alkali-soluble resins A1: Novolak resin having a phenolic hydroxyl group and an imide group (an acid-catalyzed reaction product of bis(2-hydroxyphenyl)4,4'-oxyphthalimide and 1,4-bismethoxymethylbenzene, weight-average molecular weight: 36,000) A2: Novolak resin having a phenolic hydroxyl group and an imide group (an acid-catalyzed reaction product of N,N'-bis(3-hydroxyphenyl)-4,4'-biphthalimide and 1,4-bismethoxymethylbenzene, weight-average molecular weight: 78,000)

[0092] (B) Imide Compound B1: Imide Compound Represented by Formula (B1) 4,4'-oxydiphthalic anhydride (5 equivalents) was dissolved in N-methylpyrrolidone by heating at 80°C. A solution containing N-methylpyrrolidone and bis(4-amino-3-carboxyphenyl)methane (4.5 equivalents) was added thereto and stirred at room temperature for 20 hours. 3-Aminophenol (1 equivalent) was then added to the reaction solution, and the reaction solution was stirred at room temperature for 5 hours. The reaction solution was then heated to 195°C and stirred for 6 hours, allowing the imidization reaction to proceed. The reaction solution was then returned to room temperature, and a precipitate was formed by reprecipitation from 2-propanol. The precipitate was filtered and dried in vacuo at 100°C to obtain the desired imide compound B1 represented by Formula (B1) (weight average molecular weight: 26,000).

[0093] B2: Imide compound represented by formula (B2)

[0123] Using 4,4'-oxydiphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 3-aminophenol, imide compound B2 (weight average molecular weight: 21,000) represented by formula (B2) was obtained in the same manner as in the synthesis of imide compound B1.

[0094] B3: Imide compound represented by formula (B3)

[0123] Using 4,4'-oxydiphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2-amino-p-cresol, imide compound B3 (weight average molecular weight: 18,000) represented by formula (B2) was obtained in the same manner as in the synthesis of imide compound B1.

[0095] (C) Photoacid Generator C1: 1-naphthoquinone-2-diazide-5-sulfonic acid ester of 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, esterification rate approximately 63%, manufactured by Daito Chemix Co., Ltd., product name "PA28"

[0096] (D) Thermal crosslinking agent D1: 4,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl]phenyl]ethylidene]bis[2,6-bis(methoxymethyl)phenol] (represented by formula (42), R ４０ is a methoxymethyl group, manufactured by Honshu Chemical Industry Co., Ltd., trade name "HMOM-TPPA")

[0097] (E) Adhesion aid E1: 5-aminotetrazole (manufactured by Toyobo Co., Ltd., trade name "HAT")

[0098] (F) Silane coupling agent F1: 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM403")

[0099] 2. Photosensitive Resin Composition Each component was mixed with ethyl lactate or the like (solvent) at the blending ratio (parts by mass) shown in Table 1 or Table 2. The mixture was filtered under pressure through a polytetrafluoroethylene filter with 0.2 μm pores to prepare a photosensitive resin composition.

[0100] 3. Evaluation (1) Opening Ability A photosensitive resin composition was spin-coated onto a silicon substrate, and the coating was heated to remove the solvent, forming a 10 μm-thick resin film made of the photosensitive resin composition. Next, using an i-line stepper (Canon, product name "FPA-3000iW"), the resin film was subjected to reduced projection exposure with i-line (365 nm) through a mask having a 5 μm × 5 μm square hole pattern. The exposure dose was 1000 mJ / cm. ２ The resin film after exposure was developed using a 2.38% TMAH aqueous solution, followed by rinsing with water. The resin film was developed under several conditions, with the development time varying between 30 and 120 seconds. The resin film after the development was observed, and the opening property was evaluated according to the following criteria: A: The development time required to form a 5 μm×5 μm opening was 30 seconds or more and less than 120 seconds; B: The development time required to form a 5 μm×5 μm opening was 120 seconds or more; C: Residue remained in the opening after a development time of 120 seconds, or the unexposed portion of the resin film was completely dissolved after a development time of less than 30 seconds.

[0101] (2) Tensile Strength of Cured Film The photosensitive resin composition was applied to a silicon substrate by spin coating, and the coating was heated to remove the solvent, forming a resin film with a thickness of 8 to 9 μm. Next, the resin film was exposed to light at all wavelengths through a mask using an aligner (manufactured by SUSS MicroTec K.K., product name "MA-8"). The exposure dose was 1500 mJ / cm. ２ After exposure, a resin film having a pattern including 10 mm-wide linear portions was formed by development using a 2.38% TMAH aqueous solution. The formed resin film was heated in an inert gas oven (INH-9CD-S) under a nitrogen atmosphere, with the temperature increased to 230°C over 1 hour and maintained at 230°C for 2 hours, thereby promoting curing of the resin film. The thickness of the cured resin film after heating was approximately 7 μm.

[0102] A 10 mm wide strip-shaped test piece was prepared from the cured film peeled off from the silicon substrate. A tensile test of the test piece was performed using an autograph AGS-100NX manufactured by Shimadzu Corporation. In the tensile test, the chuck distance was 20 mm, the tensile speed was 5 mm / min, and the temperature of the measurement environment was room temperature (20°C to 25°C). Tensile tests were performed on six test pieces for each level. The tensile strength was determined from the results of the tensile test. The maximum tensile strength of the six test pieces is shown in Table 1.

[0103] (3) Glass Transition Temperature (Tg) of Cured Film Test pieces measuring 10 mm in width, 30 mm in length, and 10 μm in thickness were cut from cured films formed in the same manner as for measuring tensile strength. The dynamic viscoelasticity of the test pieces was measured using a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Corporation) by increasing the temperature from 30° C. to 380° C. at a rate of 5° C. / min. The temperature at which tan δ reached a maximum was taken as the glass transition temperature.

[0104] (4) Coefficient of Linear Expansion (CTE) of Cured Films Test specimens measuring 4 mm wide, 30 mm long, and 10 μm thick were cut from cured films formed using the same procedure as for the cured films used to measure tensile strength. The dimensional change of the resulting test specimens due to temperature change was measured using a thermomechanical analyzer (manufactured by Hitachi High-Tech Corporation, product name "TMA7100") in tension mode under atmospheric conditions, with the temperature rising from 30°C to 380°C at a rate of 5°C / min. From the measurement results, the coefficient of linear expansion (CTE) of the test specimens (cured films) in the range of 100 to 150°C was calculated.

[0105]

[0106]

[0107] (5) Results The results are shown in Tables 1 and 2. A comparison of Comparative Example 1 with Examples 1-1 to 1-5 confirmed that the incorporation of an imide compound improved the opening properties for pattern formation by development, as well as improved the tensile strength and heat resistance of the cured film. A comparison of Comparative Example 2 with Example 2 also confirmed similar trends.

[0108] 10...semiconductor chip, 11...chip main body portion, 12...pad portion, 13...protective film, 20...wiring portion, 31...conductor wiring layer, 32...connection portion, 33...barrier metal, 41...surface protection layer (insulating layer), 42...cover coat layer (insulating layer), 50...conductive ball, 100...semiconductor device

Claims

1. A composition comprising: (A) an alkali-soluble resin; (B) an imide compound; (C) a photoacid generator which is a compound that generates an acid by light; and (D) a thermal crosslinker which is a compound that crosslinks the alkali-soluble resin by heat, wherein the alkali-soluble resin is represented by the following formula (I): The resin includes a structural unit which is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by the following formula (II): In formula (I), R １ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z １ is a tetravalent organic group, and two R １ may be the same or different, and in formula (II), R ２ is a monovalent organic group, and Z ２ is a tetravalent organic group, X is a divalent organic group, and n is an integer of 1 or more.

2. R ２ 2. The positive photosensitive resin composition according to claim 1, wherein is a hydroxyphenyl group optionally substituted with an alkyl group.

3. The imide compound is represented by the following formula (II'): In formula (II′), R ２ , X and n are R in formula (II) ２ , X and n are defined as ４ The positive photosensitive resin composition according to claim 1 , wherein is a divalent organic group or a covalent bond.

4. A composition comprising: (A) an alkali-soluble resin; (C) a photoacid generator which is a compound that generates an acid by light; and (D) a thermal crosslinker which is a compound that crosslinks the alkali-soluble resin by heat, wherein the alkali-soluble resin is represented by the following formula (I): a first constitutional unit which is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by the following formula (III): and a second structural unit which is a group obtained by removing one or more hydrogen atoms from a bisphenolimide compound represented by formula (I): １ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z １ is a tetravalent organic group, and two R １ may be the same or different, and in formula (III), R ３ is a hydroxyphenyl group optionally substituted with an alkyl group, and Z ２ is a tetravalent organic group, X is a divalent organic group, n is an integer of 1 or more, and a plurality of R ３ , Z ２ and X may be the same or different.

5. The bisphenolimide compound represented by the formula (III) is a bisphenolimide compound represented by the following formula (III'): In formula (III′), R ３ , X and n are R in formula (III) ３ , X and n are defined as ４ The positive photosensitive resin composition according to claim 4, wherein is a divalent organic group or a covalent bond.

6. The positive photosensitive resin composition according to claim 4, wherein the resin comprises a first component having a polymer chain containing the first structural unit, and a second component different from the first component having a polymer chain containing the second structural unit.

7. The positive photosensitive resin composition according to claim 1 or 4, wherein X is a divalent group having an aromatic group substituted with a hydroxy group, a carboxy group, or both of these groups.

8. X is represented by the following formula (10): In formula (10), Z is a divalent group represented by ５ is a divalent organic group or a covalent bond, and Z ６ and Z ７ The positive photosensitive resin composition according to claim 1 or 4, wherein each independently represents a hydroxy group or a carboxy group.

9. The bisphenolimide compound represented by formula (I) is a compound represented by formula (I'): In formula (I′), R １ is R in formula (I) １ is defined similarly to Z ３ The positive photosensitive resin composition according to claim 3 or 5, wherein is a divalent organic group or a covalent bond.

10. The positive photosensitive resin composition according to claim 1 or 4, wherein the resin is a novolak resin further containing a structural unit derived from a reactive compound selected from the group consisting of an aldehyde compound, a compound having multiple methoxymethyl groups, and a compound having multiple hydroxymethyl groups.

11. The positive photosensitive resin composition according to claim 1 or 4, wherein the thermal crosslinking agent comprises an alkoxy compound having a plurality of alkoxy groups.

12. A method for forming an insulating resin film, comprising: exposing a portion of a photosensitive layer containing the positive photosensitive resin composition according to claim 1 or 4 to light; forming an insulating resin film having a pattern including openings by developing to remove a portion of the photosensitive layer; and heating the insulating resin film.

13. An insulating resin film comprising a cured product of the positive photosensitive resin composition according to claim 1 or 4, and having a pattern including openings.

14. A semiconductor device comprising: a semiconductor chip; and a wiring section including a conductor wiring layer connected to the semiconductor chip and one or more insulating layers, wherein at least a portion of the one or more insulating layers is the insulating resin film according to claim 13.

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