Positive photosensitive resin composition, insulating resin film, method of forming insulating resin film, semiconductor device, imide compound, and alkali-soluble resin

Abstract

Provided is a positive photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a thermal crosslinking agent. The alkali-soluble resin has a polymer chain containing an imide-based structural unit which is a group formed by removing one or more hydrogen atoms from an imide compound represented by formula (I). X1 and X2 are each independently a monovalent group represented by formula (11) or (12). C1, C2, C3, C4, Z1, and Z2 form a first tetravalent group which is a 5-membered cyclic group, or a second tetravalent group containing a cyclic group containing two or more cyclic portions.　

Description

Positive photosensitive resin composition, insulating resin film, method for forming insulating resin film, semiconductor device, imide compound, and alkali-soluble resin

[0001] The present disclosure relates to a positive-type photosensitive resin composition, an insulating resin film, a method for forming an insulating resin film, a semiconductor device, an imide compound, and an alkali-soluble resin.

[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-type photosensitive resin composition that contains an alkali-soluble resin having an imide group and a phenolic hydroxyl group, and that can form a cured film that maintains high adhesion even in a high-temperature, high-humidity environment.

[0005] The present disclosure includes the following: [1] A photopolymerizable composition comprising: (A) an alkali-soluble resin; (B) a photoacid generator that generates an acid by light; and (C) a thermal crosslinker that crosslinks the alkali-soluble resin by heat, wherein the alkali-soluble resin is represented by the following formula (I): In formula (I), X has a polymer chain containing an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from an imide compound represented by formula (I). １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３and R ５ At least one of the C groups is a hydrogen atom; １ , C ２ , C ３ and C ４ are each independently a carbon atom which may be bonded to a hydrogen atom, Z １ and Z ２ are each independently a group containing a hydrocarbon group or a covalent bond, １ , C ２ , C ３ , C ４ , Z １ and Z ２ is a first tetravalent group which is a 5-membered or 6-membered cyclic group, or a second tetravalent group which contains a cyclic group containing two or more cyclic moieties, wherein the two or more cyclic moieties may form a fused ring, a spiro ring, or a bridged ring, and the two or more cyclic moieties may be bonded to each other via a linking group or a covalent bond, and the linking group is -C(R ２１ ) (R ２２ )- and R ２１ and R ２２ [2] A positive photosensitive resin composition, wherein the imide compound is a divalent group represented by the following formula (IA): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, j is an integer of 0 to 3, and k is an integer of 0 to 4. [3] The positive photosensitive resin composition according to [1], wherein the imide compound is represented by the following formula (IB): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０may be the same or different, and k is an integer of 0 to 4. [4] The positive photosensitive resin composition according to [1], wherein the imide compound is represented by the following formula (IC): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １２ and R １３ are each independently an alkanediyl group having 1 to 3 carbon atoms which may have a substituent, or a covalent bond, and R １２ and R １３ [5] The positive photosensitive resin composition according to claim 1, wherein the imide compound is a compound represented by the following formula (ID): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R ２３ and R ２４ are each independently a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a hydrogen atom, and R ２３ and R ２４ may be bonded to each other to form a 3- to 8-membered cyclic group. [6] The positive photosensitive resin composition according to [1], wherein the imide compound is represented by the following formula (IE): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R ２１ and R ２２ [7] The positive photosensitive resin composition according to [1], wherein each of the imide compounds is a compound represented by the following formula (IF): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０may be the same or different, and m is an integer of 0 to 2. [8] The positive photosensitive resin composition according to [1], wherein the imide compound is represented by the following formula (1G): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and j is an integer of 0 to 3. [9] The positive photosensitive resin composition according to [1], wherein the imide compound is represented by the following formula (1H): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０may be the same or different, and k is an integer of 0 to 4.

[10] The alkali-soluble resin according to any one of [1] to [9], wherein the polymer chain further contains 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] A method for forming an insulating resin film, comprising: exposing a part of a photosensitive layer containing the positive photosensitive resin composition according to any one of [1] to [9]; forming an insulating resin film having a pattern including openings by development that removes part of the photosensitive layer; and heating the insulating resin film.

[12] An insulating resin film, comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [9], and having a pattern including openings.

[13] A semiconductor device, comprising: a semiconductor chip; and a wiring portion 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

[12] .

[14] An imide compound represented by the above formula (IA).

[15] An imide compound represented by the above formula (IB).

[16] An imide compound represented by the above formula (IC).

[17] An imide compound represented by the above formula (ID).

[18] An imide compound represented by the above formula (IE).

[19] An imide compound represented by the above formula (IF).

[20] An imide compound represented by the above formula (IG).

[21] An imide compound represented by the above formula (IH).

[22] An alkali-soluble resin having a polymer chain containing an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from the imide compound according to any one of

[14] to

[21] .

[23] The alkali-soluble resin according to

[22] , wherein the polymer chain further contains 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.

[0006] A positive-type photosensitive resin composition can be provided that contains an alkali-soluble resin having an imide group and a phenolic hydroxyl group, and that can form a cured film that maintains high adhesion even in a high-temperature, high-humidity environment. The cured film can also have high heat resistance.

[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 An example of the alkali-soluble resin has a polymer chain containing an imide-based structural unit, which is a group obtained by removing one or more hydrogen atoms from an imide compound represented by the following formula (I): １ and X ２ are each independently a monovalent group represented by the following formula (11) or (12):

[0011] In formula (11), R ２ , R ３ , R４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), and R ２ or R ４ At least one of R is a hydrogen atom. １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), and R １ , R ３ and R ５ At least one of them is a hydrogen atom. The group represented by formula (11) may be a group represented by the following formula (11A) or (11B). The group represented by formula (12) may be a group represented by the following formula (12A) or (12B).

[0012] In formula (I), C １ , C ２ , C ３ and C ４ are each independently a carbon atom which may be bonded to a hydrogen atom, Z １ and Z ２ are each independently a group containing a hydrocarbon group or a covalent bond. １ and C ２ may be bonded to each other via saturated or unsaturated bonds. ３ and C ４ may be bonded to each other via saturated or unsaturated bonds. １ is a group containing a hydrocarbon group, Z １ is C １ and C ４ Z can be bonded to Z via a saturated or unsaturated bond. ２ is a group containing a hydrocarbon group, Z ２ is C ２ and C ３ Z can be bonded to Z via a saturated or unsaturated bond. １ is a covalent bond, C １ and C ４ may be directly bonded to each other via a saturated or unsaturated bond. ２ is a covalent bond, C２ and C ３ may be directly bonded to each other via a saturated or unsaturated bond.

[0013] C １ , C ２ , C ３ , C ４ , Z １ and Z ２ can be a group of atoms forming a first tetravalent group that is a five- or six-membered cyclic group, or a second tetravalent group that includes a cyclic group that includes two or more cyclic moieties. The first tetravalent group and the second tetravalent group have a rigid structure, which is thought to contribute to maintaining high adhesion in a high-temperature, high-humidity environment.

[0014] C １ , C ２ , C ３ , C ４ , Z １ and Z ２ The first tetravalent group containing C is a 5- or 6-membered cyclic group, and may be, for example, a cyclopentane ring which may have a substituent, a benzene ring which may have a substituent, or a cyclohexane ring which may have a substituent. １ , C ２ , C ３ , C ４ , Z １ and Z ２ When X forms the first tetravalent group, the imide compound may be, for example, a compound represented by the following formula (ID) or (1F): １ and X ２ represents X in formula (I). １ and X ２ R in formula (ID) is defined as ２３ and R ２４ are each independently a hydrocarbon group having 1 to 8 carbon atoms (e.g., a methyl group) which may have a substituent, or a hydrogen atom, and R ２３ and R ２４ may be bonded to each other to form a cyclic group having 3 to 8 members. １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and m is an integer of 0 to 2.

[0015] C １ , C ２ , C ３ , C ４ , Z １ and Z ２ The second tetravalent group containing the group includes a cyclic group containing two or more cyclic moieties. The two or more cyclic moieties may form a fused ring, a spiro ring, or a bridged ring. The two or more cyclic moieties may be bonded to each other via a linking group or a covalent bond. The linking group here is -C(R ２１ ) (R ２２ )-, and R ２１ and R ２２ are each independently a hydrogen atom or a methyl group. Each cyclic moiety constituting the second tetravalent group may be a 3- to 8-membered ring or a 5- or 6-membered aromatic group or an alicyclic group. The second tetravalent group may contain a group obtained by removing one or more hydrogen atoms from the following cyclic compounds:

[0016] C １ , C ２ , C ３ , C ４ , Z １ and Z ２ When forms the second tetravalent group, the imide compound may be, for example, a compound represented by the following formula (IA), (IB), (IC) or (IG).

[0017] X in formulas (IA), (IB), (IC) and (IG) １ and X ２ represents X in formula (I). １ and X ２ In formulae (IA), (IB) and (IG), R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, j is an integer of 0 to 3, and k is an integer of 0 to 4. In formula (1C), R １２ and R １３are each independently an alkanediyl group having 1 to 3 carbon atoms which may have a substituent, or a covalent bond, and R １２ and R １３ A cyclic group having 3 to 8 members including R １２ may be an alkanediyl group (for example, a carbonyl group) substituted with an oxo group (=O).

[0018] C １ , C ２ , C ３ , C ４ , Z １ and Z ２ does not form a fused ring, a spiro ring, or a bridged ring, and ２１ ) (R ２２ )- or a cyclic moiety that is not bonded to another cyclic moiety via a covalent bond. Examples of imide compounds in which the second tetravalent group contains such a cyclic moiety include compounds represented by the following formula (1E) or (1H). X in formulas (IE) and (IH) １ and X ２ represents X in formula (I). １ and X ２ R in formula (IE) is defined as ２１ and R ２２ are each independently a hydrogen atom or a methyl group. １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and k is an integer of 0 to 4.

[0019] The alkali-soluble resin may be a novolac resin having a polymer chain containing an imide-based structural unit derived from an imide compound represented by formula (I). The polymer chain of the novolac resin may contain, for example, an imide-based structural unit derived from a bisphenolimide compound represented by formula (I) and a structural unit (hereinafter sometimes referred to as an "addition 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 imide-based structural unit and the addition unit may be bonded alternately. The imide-based structural unit may be a residue obtained by removing one or more hydrogen atoms from a benzene ring to which a phenolic hydroxyl group is bonded in an imide compound. The imide-based structural unit 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.

[0020] 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.

[0021] 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.

[0022] The following formula is an example of a partial structure of a polymer chain that can be possessed by a novolak resin containing an imide-based structural unit and an additional unit derived from a reactive compound. The polymer chain in this example is represented by formula (IA), and X １ and X ２ is a group represented by formula (11A), and an additional unit derived from a compound represented by formula (21).

[0023] Novolac resins having polymer chains containing imide-based structural units derived from imide 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 an imide 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 imide 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 imide 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 imide 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 %.

[0024] When the alkali-soluble resin is one or more resins having a polymer chain containing imide-based structural units and additional units (e.g., novolac resin), the proportion of the additional units relative to the total amount of the imide-based structural units and additional units may be 1% by mass or more and 90% by mass or less, 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.

[0025] 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.

[0026] (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.

[0027] 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.

[0028] 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.

[0029] 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).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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 content of the alkali-soluble resin.

[0036] (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.

[0037] 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.

[0038] 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.

[0039] 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 may be considered a thermal crosslinking agent rather than an alkali-soluble resin. An alkoxy compound having an alkoxy group and a phenolic hydroxyl group may contribute to improving the sensitivity of a photosensitive resin composition.

[0040] 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.

[0041] 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).

[0042] 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:

[0043] 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 content of the alkali-soluble resin, from the viewpoints of the heat resistance of the insulating resin film (cured film) and suppression of warping.

[0044] In the photosensitive resin composition, the total content of the (A) alkali-soluble resin, the (B) photoacid generator, and the (C) 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.

[0045] 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 promoter, 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).

[0046] 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.

[0047] 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.

[0048] 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).

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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).

[0058] 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.

[0059] 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).

[0060] 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).

[0061] 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).

[0062] 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).

[0063] 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).

[0064] Method for forming an insulating resin film having a pattern: 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] The semiconductor device insulating resin film may be, for example, an insulating layer constituting a wiring portion of the 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] [Examples] The present invention is not limited to the following examples. 1. Raw Materials (A) Alkali-Soluble Resin A1: A reaction product of an imide compound ODPA / 1 represented by the following formula with 1,4-bismethoxymethylbenzene (PXDM) in the presence of p-toluenesulfonic acid (weight average molecular weight: 36,000).

[0078] A2: A reaction product of the imide compound HQDA / 2 represented by the following formula with 1,4-bismethoxymethylbenzene (PXDM) in the presence of p-toluenesulfonic acid (weight average molecular weight: 42,000).

[0079] A3: A reaction product of the imide compound TMEG / 3 represented by the following formula with 1,4-bismethoxymethylbenzene (PXDM) in the presence of p-toluenesulfonic acid (weight average molecular weight: 34,000).

[0080] A4: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF, 1 equivalent) was dissolved in 1,3-dimethyl-2-imidazolidinone. 2-Amino-p-cresol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. Subsequently, the reaction solution was heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound BPAF / 1. The imide compound BPAF / 1 and 1,4-bismethoxymethylbenzene (PXDM) were reacted in the presence of p-toluenesulfonic acid (PTS) at 180°C for 20 hours to yield alkali-soluble resin A4 (weight average molecular weight: 27,000), which was a reaction product (novolac resin) of BPAF / 1 and PXDM.

[0081] A5: Imide compound BPAF / 2 was obtained in the same manner as for BPAF / 1, except that 2-aminophenol was used instead of 2-amino-p-cresol. Alkali-soluble resin A5 (weight average molecular weight: 10,000), which was a reaction product (novolak resin) of BPAF / 2 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that the obtained imide compound BPAF / 2 was used.

[0082] A6 Tetralin dianhydride (TDA, 1 equivalent) was dissolved in γ-butyrolactone. 3-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound TDA / 3. Alkali-soluble resin A6 (weight average molecular weight: 20,000), which is a reaction product (novolac resin) of TDA / 3 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that imide compound TDA / 3 was used.

[0083] A7 Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (CpODA, 1 equivalent) was dissolved in γ-butyrolactone. 2-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound CpODA / 2. Alkali-soluble resin A7 (weight-average molecular weight: 13,000), which is a reaction product (novolac resin) of CpODA / 2 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that imide compound CpODA / 2 was used.

[0084] A8 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA, 1 equivalent) was dissolved in γ-butyrolactone. 2-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound CPDA / 2. Alkali-soluble resin A8 (weight average molecular weight: 11,000), which was a reaction product (novolac resin) of CPDA / 2 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that imide compound CPDA / 2 was used.

[0085] A9: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA, 1 equivalent) was dissolved in γ-butyrolactone. 3-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound BPADA / 3. Alkali-soluble resin A9 (weight average molecular weight: 184,000), which is a reaction product (novolac resin) of BPADA / 3 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that imide compound BPADA / 3 was used.

[0086] A10 Pyromellitic anhydride (PMDA, 1 equivalent) was dissolved in γ-butyrolactone. 3-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound PMDA / 3. Alkali-soluble resin A10 (weight average molecular weight: 23,000), which is a reaction product (novolac resin) of PMDA / 3 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that imide compound PMDA / 3 was used.

[0087] A11 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 1 equivalent) was dissolved in 1,3-dimethyl-2-imidazolidinone. 2-Amino-p-cresol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound BPDA / 1. Alkali-soluble resin A11 (weight average molecular weight: 13,000), which is a reaction product (novolac resin) of BPDA / 1 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that imide compound BPDA / 1 was used.

[0088] A12 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl]-4,4'-diyl bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (TMPBP, 1 equivalent) was dissolved in γ-butyrolactone. 2-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. The reaction solution was then heated to 180°C and stirred for 4 hours, allowing the imidization reaction to proceed, yielding imide compound TMPBP / 2. Alkali-soluble resin A12 (weight average molecular weight: 10,000), which is a reaction product (novolak resin) of TMPBP / 2 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that the obtained imide compound TMPBP / 2 was used.

[0089] A13: Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BcODA, 1 equivalent) was dissolved in γ-butyrolactone. 2-Aminophenol (2 equivalents) was added thereto, and the reaction solution was stirred at room temperature for 1 hour. Subsequently, the reaction solution was heated to 180°C and stirred for 4 hours, thereby allowing the imidization reaction to proceed, yielding imide compound BcODA / 2. Alkali-soluble resin A12 (weight-average molecular weight: 24,000), which is a reaction product (novolak resin) of BcODA / 2 and PXDM, was obtained in the same manner as for alkali-soluble resin A4, except that the imide compound BcODA / 2 was used.

[0090] (B) Photoacid Generator B1: 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 90%, manufactured by Daito Chemix Co., Ltd., product name "PA28"

[0091] (C) Thermal crosslinking agent C1: 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")

[0092] (D) Adhesion aid D1: 5-aminotetrazole (manufactured by Toyobo Co., Ltd., trade name "HAT")

[0093] (E) Silane coupling agent E1: 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM403")

[0094] 2. Photosensitive resin composition: 100 parts by mass of any one of alkali-soluble resins A1 to A13, 12 parts by mass of a photoacid generator, 25 parts by mass of a thermal crosslinking agent, 2 parts by mass of an adhesion aid, and 1 part by mass of a silane coupling agent were mixed with ethyl lactate (solvent). The mixture was pressure-filtered through a polytetrafluoroethylene filter with 0.2 μm pores to prepare a photosensitive resin composition.

[0095] 3. Evaluation (1) Glass Transition Temperature (Tg) 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 12 μm. The formed resin film was then 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 10 μm.

[0096] A test piece measuring 4 mm in width, 25 mm in length, and 10 μm in thickness was cut from the cured film peeled from the silicon substrate. The obtained test piece was subjected to thermomechanical analysis using a thermomechanical analyzer (manufactured by Hitachi High-Technologies Corporation) under the condition of heating from 30° C. to 380° C. at a rate of 5° C. / min to determine Tg.

[0097] The adhesive photosensitive resin composition after the PCT test was spin-coated onto a silicon substrate. The coating was heated at 120°C for 3 minutes to form a photosensitive layer (insulating resin film) with a thickness of 5.5 to 6 μm. Next, using an inert gas oven (INH-9CD-S), the temperature was raised to 230°C over 1 hour under a nitrogen atmosphere and maintained at 230°C for 2 hours to promote curing of the insulating resin film. The thickness of the cured insulating resin film after heating was approximately 5 μm. The laminate of the silicon substrate and the cured film was subjected to a PCT test in which the laminate was left in an environment at a temperature of 121°C and humidity of 100% for 100 hours. The adhesion of the cured film to the silicon substrate before and after the PCT test was evaluated by the following cross-cut test. Cross-cut test: Using a cutter knife, eleven parallel linear cuts were made at 1 mm intervals in the center of the cured film surface along orthogonal vertical or horizontal directions. The cured film has an area of ​​1 cm ２ The area was divided into 100 square portions surrounded by cuts. The cuts were formed by moving the cutter knife at a constant speed for about 0.5 seconds per cut, while keeping the angle between the cutting edge of the cutter knife and the surface of the cured film constant within the range of 35 to 45 degrees, so that the cutter knife penetrated the cured film and reached the silicon substrate. The cured film divided by the cuts was observed, and the number of the 100 cured film pieces that peeled off from the silicon substrate was confirmed. Before the PCT test, no peeling of the cured film was observed at any level.

[0098]

[0099] The evaluation results are shown in Table 1. The cured films formed from the photosensitive resin compositions of the examples containing alkali-soluble resins containing structural units derived from the imide compound represented by formula (I) maintained high adhesion after the PCT test under a high-temperature, high-humidity environment.

[0100] 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) a photoacid generator which is a compound that generates an acid by exposure to light; and (C) 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): In formula (I), X has a polymer chain containing an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from an imide compound represented by formula (I). １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of the C groups is a hydrogen atom; １ , C ２ , C ３ and C ４ are each independently a carbon atom which may be bonded to a hydrogen atom, Z １ and Z ２ are each independently a group containing a hydrocarbon group or a covalent bond, １ , C ２ , C ３ , C ４ , Z １ and Z ２ is a first tetravalent group which is a 5-membered or 6-membered cyclic group, or a second tetravalent group which contains a cyclic group containing two or more cyclic moieties, wherein the two or more cyclic moieties may form a fused ring, a spiro ring, or a bridged ring, and the two or more cyclic moieties may be bonded to each other via a linking group or a covalent bond, and the linking group is -C(R ２１ ) (R ２２ )- and R ２１ and R ２２ and each independently form a divalent group and a second tetravalent group, each of which is a hydrogen atom or a methyl group.

2. The imide compound is represented by the following formula (IA): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, j is an integer of 0 to 3, and k is an integer of 0 to 4.

3. The imide compound is represented by the following formula (IB): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and k is an integer of 0 to 4.

4. The imide compound is represented by the following formula (IC): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １２ and R １３ are each independently an alkanediyl group having 1 to 3 carbon atoms which may have a substituent, or a covalent bond, and R １２ and R １３ 2. The positive photosensitive resin composition according to claim 1, wherein a 3- to 8-membered cyclic group comprising the following is formed.

5. The imide compound is represented by the following formula (ID): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R ２３ and R ２４ are each independently a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a hydrogen atom, and R ２３ and R ２４ may be bonded to each other to form a cyclic group having 3 to 8 members.

6. The imide compound is represented by the following formula (IE): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R ２１ and R ２２ The positive photosensitive resin composition according to claim 1 , wherein each independently represents a hydrogen atom or a methyl group.

7. The imide compound is represented by the following formula (IF): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and m is an integer of 0 to 2.

8. The imide compound is represented by the following formula (IG): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and j is an integer of 0 to 3. The positive photosensitive resin composition according to claim 1, 9. The imide compound is represented by the following formula (IH): is a compound represented by the formula: １ and X ２ is X in formula (I) １ and X ２ is defined similarly to R １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and k is an integer of 0 to 4.

10. The positive photosensitive resin composition according to claim 1, wherein the polymer chain further contains 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. 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 claims 1 to 10; 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.

12. An insulating resin film comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 10, and having a pattern including openings.

13. 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 described in claim 12.

14. Formula (IA): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, j is an integer of 0 to 3, and k is an integer of 0 to 4.

15. Formula (IB): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and k is an integer of 0 to 4.

16. The following formula (IC): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; １２ and R １３ are each independently an alkanediyl group having 1 to 3 carbon atoms which may have a substituent, or a covalent bond, and R １２ and R １３ An imide compound in which a 3- to 8-membered cyclic group containing the following is formed.

17. The following formula (ID): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; ２３ and R ２４ are each independently a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a hydrogen atom, and R ２３ and R ２４ may be bonded to each other to form a 3- to 8-membered cyclic group.

18. The following formula (IE): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; ２１ and R ２２ are each independently a hydrogen atom or a methyl group.

19. The following formula (IF): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and m is an integer of 0 to 2.

20. The following formula (IG): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom; １０ is an alkyl group having 1 to 3 carbon atoms, and multiple R １０ may be the same or different, and j is an integer of 0 to 3.

21. The following formula (1H): An imide compound represented by the formula: X １ and X ２ are each independently represented by the following formula (11) or (12): In formula (11), R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ２ or R ４ At least one of R is a hydrogen atom, １ , R ３ , R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １ , R ３ and R ５ At least one of R is a hydrogen atom, and multiple R in the same molecule １０ may be the same or different, and k is an integer of 0 to 4.

22. An alkali-soluble resin having a polymer chain containing an imide-based structural unit, which is a group formed by removing one or more hydrogen atoms from the imide compound according to any one of claims 14 to 21.

23. The alkali-soluble resin according to claim 22, wherein the polymer chain further contains 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.

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