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

Abstract

A positive photosensitive resin composition according to the present invention comprises (A) an alkali-soluble resin, (B) a photoacid generator, which is a compound that generates an acid when exposed to light, and (C) a thermal crosslinking agent, which is a compound that induces the crosslinking of the alkali-soluble resin when exposed to heat. The alkali-soluble resin has a polymer chain containing an imide-based constituent unit which is a group obtained by removing one or more hydrogen atoms from an imide compound represented by formula (I).

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 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, Japanese Patent Application Laid-Open No. 2007-57595

[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 capable of forming a pattern by development in a shorter time using an alkali developer.

[0005] The present disclosure includes the following. [1] (A) An alkali-soluble resin, (B) A photoacid generator which is a compound that generates an acid by light, (C) A thermal crosslinking agent which is a compound that crosslinks the alkali-soluble resin by heat, and the alkali-soluble resin contains an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from an imide compound represented by the formula (I): and has a polymer chain, and in the formula (I), X １ and X ２ are each independently a monovalent group represented by the formula (11) or (12): In the 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 at least one of R ２ or R ４ is a hydrogen atom, and in the formula (12), R 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 them is a hydrogen atom, L is a covalent or divalent organic group, and R １０ However, it is an alkyl group having 1 to 3 carbon atoms, and multiple Rs in the same molecule １０ Positive-type photosensitive resin composition in which the two elements may be the same or different, and m and n are each independently integers from 0 to 3. [2] L is a covalent bond, an oxy group, or formula (15): or (16): It is a divalent group represented by R ６ and R ７ The positive-type photosensitive resin composition according to [1], wherein each is independently an alkylene group having 1 to 3 carbon atoms, an arylene group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or a group which comprises two or more arylene groups which may be substituted with an alkyl group having 1 to 3 carbon atoms and a covalent bond or alkylene group having 1 to 3 carbon atoms linking two or more of the arylene groups. [3] The positive-type photosensitive resin composition according to [1] or [2], wherein the polymerization chain further comprises a constituent unit derived from a reactive compound selected from an aldehyde compound, a compound having a plurality of methoxymethyl groups, and a compound having a plurality of hydroxymethyl groups. [4] A method for forming an insulating resin film, comprising: exposing a part of a photosensitive layer containing the positive-type photosensitive resin composition according to any one of [1] to [3]; developing to remove a part of the photosensitive layer to form an insulating resin film having a pattern including openings; and heating the insulating resin film. [5] An insulating resin film comprising a cured product of a positive-type photosensitive resin composition according to any one of [1] to [3], and having a pattern including openings. [6] A semiconductor device comprising: a semiconductor chip; a wiring portion comprising 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 [5]. [7] Formula (I): It is expressed as follows, and in equation (I), X １ and X ２ These are independently given by equation (11) or (12): It is a monovalent group represented by formula (11), where R ２ , R ３ , R４ and R ５ However, each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ２ or R ４ At least one of them is a hydrogen atom, and in formula (12), R １ , R ３ , R ４ and R ５ However, each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R １ , R ３ and R ５ At least one of them is a hydrogen atom, L is a covalent or divalent organic group, and R １０ However, it is an alkyl group having 1 to 3 carbon atoms, and multiple Rs in the same molecule １０ An imide compound in which m and n are integers from 0 to 3, and which may be the same or different, and m and n are each independently integers from 0 to 3. [8] L is a single bond, an oxy group, or formula (15) or (16): It is a divalent group represented by R ６ and R ７ The imide compound according to [7], wherein each is independently an alkylene group having 1 to 3 carbon atoms, an arylene group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or a group which comprises two or more arylene groups which may be substituted with an alkyl group having 1 to 3 carbon atoms and a covalent bond or alkylene group having 1 to 3 carbon atoms linking two or more of the arylene groups. [9] An alkali-soluble resin having a polymerization chain comprising an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from the imide compound according to [7] or [8].

[10] The alkali-soluble resin according to [9], wherein the polymerization chain further comprises structural units derived from a reactive compound selected from an aldehyde compound, a compound having a plurality of methoxymethyl groups, and a compound having a plurality of hydroxymethyl groups.

[0006] A positive-type photosensitive resin composition can be provided that contains an alkali-soluble resin having imide groups and phenolic hydroxyl groups, and can form a pattern by developing in a shorter time using an alkaline developer.

[0007] This is a flowchart showing an example of a method for forming an insulating resin film having a pattern. This is a partial cross-sectional view showing an example of a semiconductor device.

[0008] The present invention is not limited to the following examples. In this disclosure, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended function of the process is achieved. The term "layer" includes not only structures that are formed on the entire surface when viewed as a plan view, but also structures that are formed on only a part of the surface. Numerical ranges indicated using "~" indicate a range that includes the numbers written before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step may be replaced with the upper or lower limit of a numerical range in another step. In numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with the values ​​shown in the examples.

[0009] A photosensitive resin composition is an example comprising an alkali-soluble resin, a photoacid generator which is a compound that generates acid upon exposure to light, and a thermal crosslinking agent which is a compound that crosslinks the alkali-soluble resin upon exposure to heat. The photosensitive resin composition may further contain a solvent. The photosensitive resin composition according to this disclosure can function as a positive-type photosensitive resin composition based on the change in solubility in an alkaline developer upon exposure. Furthermore, a film containing the photosensitive resin composition according to this disclosure can be thermally cured mainly by a crosslinking reaction between the thermal crosslinking agent and the alkali-soluble resin to form an insulating resin film which is a cured film containing a cured product of the photosensitive resin composition.

[0010] (A) Alkali-soluble resins An example of an alkali-soluble resin has a polymerization 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). In formula (I), X １ and X ２Each of these is an independent monovalent group represented by formula (11) or (12) below. In the imide compound represented by formula (I), the condensed ring containing the imide group is linked in an asymmetric positional relationship via L. Therefore, the polymerization chain containing the imide system constituent units derived from this imide compound forms a complex three-dimensional conformation, suppressing stacking of polymerization chains. As a result, it is thought that the alkali-soluble resin dissolves more easily in an alkaline developer in a short time.

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

[0012] In formula (I), L is a covalent bond or a divalent organic group, and R １０ However, these are alkyl groups having 1 to 3 carbon atoms. Multiple R groups within the same molecule. １０ They may be the same or different. m and n are each independent integers from 0 to 3. m and n may also be 0.

[0013] L may be a covalent bond, an oxy group (-O-), or a divalent group represented by the following formulas (15) or (16).

[0014] In equations (15) and (16), R ６and R ７ However, each of these groups independently comprises an alkylene group having 1 to 3 carbon atoms (e.g., methanediyl group, ethane-1,2-diyl group), an arylene group which may be substituted with an alkyl group having 1 to 3 carbon atoms (e.g., phenylene group), or two or more arylene groups which may be substituted with an alkyl group having 1 to 3 carbon atoms (e.g., phenylene group) and a covalent bond linking two or more of the aforementioned arylene groups or an alkylene group having 1 to 3 carbon atoms (e.g., methanediyl group, ethane-1,2-diyl group, propane-2,2-diyl group). The group comprising two or more arylene groups and a covalent bond linking two or more arylene groups or an alkylene group having 1 to 3 carbon atoms may be represented, for example, by the following formula (17). In formula (17), R ８ R is a covalent bond or an alkylene group having 1 to 3 carbon atoms (e.g., methanediyl group, ethane-1,2-diyl group, propane-2,2-diyl group), １０ However, these are alkyl groups having 1 to 3 carbon atoms. Multiple R groups within the same molecule. １０ They may be the same or different. r and s are each independent integers from 0 to 4. r and s may also be 0.

[0015] Specific examples of imide compounds represented by formula (I) include the compounds represented by the following formulas (101), (102), (103), (104), or (105). In these formulas, X １ , X ２ , R １０ , m and n are X in equation (I) １ , X ２ , R １０ , is defined similarly to m and n.

[0016] The alkali-soluble resin may be a novolac resin having a polymerization chain containing imide-based structural units derived from an imide compound represented by formula (I). The polymerization chain of the novolac resin may include, for example, imide-based structural units derived from a bisphenolimide compound represented by formula (I), and structural units (hereinafter sometimes referred to as "additional units") derived from a reactive compound selected from an aldehyde compound, a compound having a plurality of methoxymethyl groups, and a compound having a plurality of hydroxymethyl groups. In the polymerization chain of the novolac resin, the imide-based structural units and additional units may be alternately bonded. 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 other structural units at the ortho or para position relative to the phenolic hydroxyl group. The polymerization chain of the novolac resin may further contain structural units derived from a phenol compound selected from phenol, o-cresol, m-cresol, and p-cresol.

[0017] 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 formulas (22) or (23). In these formulas, R １０ R represents an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group). Multiple R in the same molecule. １０ The two groups may be the same or different. p represents an integer from 0 to 4, and q and r each independently represent an integer from 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 is 2,6-bis(hydroxymethyl)-p-cresol.

[0018] The residue derived from formaldehyde is usually a methylene group. The residue derived from a compound having two or more methoxymethyl groups can be a divalent group represented by, for example, the following formula (22A) or (23B). R in formulas (22A) and (23B) １０ , p, q and r are R in equations (22) and (23). １０ It is defined similarly to p, q, and r.

[0019] The following formula is an example of a partial structure of a polymerization chain that a novolac resin containing imide-based structural units and addition units derived from reactive compounds may have. The polymerization chain in this example is represented by formula (I), and X １ and X ２ It includes an imide system constituent unit derived from an imide compound in which is a group represented by formula (11A), and an addition unit derived from a compound represented by formula (21).

[0020] Novolac resins having polymerization chains containing imide-based structural units derived from imide compounds can be synthesized, for example, by methods similar to those used for the synthesis of 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 phenol compound component containing an imide compound represented by formula (I) and a reactive compound selected from aldehyde compounds, compounds having multiple methoxymethyl groups, and compounds having multiple hydroxymethyl groups. The phenol compound component may further contain phenol compounds selected from phenol, o-cresol, m-cresol, and p-cresol. The proportion of the imide compound in the phenol 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 phenol compound component. A higher proportion of the imide compound tends to yield particularly excellent effects in terms of good shape and high resolution of the insulating resin film. From a similar 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 component, and may be substantially 100 mol%.

[0021] When the alkali-soluble resin is one or more resins (e.g., novolac resin) having a polymerization chain containing imide-based structural units and additional units, the ratio of additional units to the total amount of imide-based structural units and additional units may be 1% by mass or more and 90% by mass or less. The ratio of additional units to the total amount of imide-based structural units and additional units may be 3% by mass or more, or 5% by mass or more, 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. The polymerization chain of the alkali-soluble resin may further contain imide-based structural units derived from an imide compound different from the imide compound represented by formula (I). In that case, the ratio of the additional units to the total amount of imide-based constituent units derived from the imide compound represented by formula (I), imide-based constituent units derived from imide compounds other than the imide compound represented by formula (I), and additional units may be within the range described above. The ratio of imide-based constituent units derived from the imide compound represented by formula (I) to the total amount of imide-based constituent units may be 10% by mass or more and 100% by mass or less, 20% by mass or more and 100% by mass or less, 30% by mass or more and 100% by mass or less, 40% by mass or more and 100% by mass or less, 50% by mass or more and 100% by mass or less, 60% by mass or more and 100% by mass or less, 70% by mass or more and 100% by mass or less, 80% by mass or more and 100% by mass or less, 90% by mass or more and 100% by mass or less, or 95% by mass or more and 100% by mass or less.

[0022] 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 balancing solubility in alkaline aqueous solutions, photosensitivity, and mechanical strength of the insulating resin film. In this disclosure, the weight-average molecular weight is a converted value based on a standard polystyrene calibration curve measured by gel permeation chromatography (GPC).

[0023] (C) Photoacid Generator The photoacid generator of component (C) contains one or more compounds that generate acid upon exposure to light (e.g., ultraviolet light), and functions as a photosensitive agent in the photosensitive resin composition. Due to the action of the acid generated from the photoacid generator upon absorption of light, the solubility in alkaline aqueous solution is selectively increased in the portion of the photosensitive layer that has been irradiated with light.

[0024] The compounds constituting the photoacid generator may be selected from compounds commonly used as photoacid generators. The compounds that generate acid upon exposure to light may be, for example, o-quinone diazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts, or a combination of two or more selected from these.

[0025] From the viewpoint of improving exposure sensitivity, the photoacid generator may contain an o-quinone diazide compound. The o-quinone diazide compound consists of an aromatic group, an oxo group (=O), and a diazide group (=N). ＋ = N － It is a compound having a oxo group and a diazide group bonded to adjacent carbon atoms in the aromatic group, respectively. The aromatic group may be, for example, a group obtained by removing a hydrogen atom from naphthalene or benzene.

[0026] The o-quinone diazide compound may have a group containing an oxo group and a diazide group, for example, a group represented by the following formulas (3a), (3b), or (3c).

[0027] Compounds having the group represented by formula (3a), (3b), or (3c) may, for example, be the 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 the group represented by formula (3a), (3b), or (3c). For example, a compound having the group represented by formula (3a) can be obtained from naphthoquinone-1,2-diazide-5-sulfonyl chloride. A compound having the group represented by formula (3b) can be obtained from naphthoquinone-1,2-diazide-6-sulfonyl chloride. A compound having the group represented by formula (3c) can be obtained from benzoquinone-1,2-diazide-4-sulfonyl chloride.

[0028] The hydroxy compounds that can be used to synthesize o-quinone diazide compounds are compounds having one or more hydroxyl groups. The residues of the hydroxy compound can be the group obtained by removing one or more hydrogen atoms from the hydroxyl group of the hydroxy compound. Examples of hydroxy compounds are 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. The compound contains 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.

[0029] Specific examples of compounds having a hydroxyl compound residue and a group represented by formula (3a), (3b), or (3c) include the compounds represented by the following formulas (31), (32), (33), (34), (35), or (36). These compounds readily absorb light in a suitable wavelength range for exposure of the photosensitive layer.

[0030] 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). In formulas (31) to (36), R ３０ R represents an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group), and multiple R groups are present in the same molecule. ３０ They may be the same or different. In equation (31), R ３１ In formula (32), each of the multiple qs represents an alkanetriyl group having 1 to 3 carbon atoms (e.g., methanetriyl group or ethane-1,1,1-triyl group), and each of the multiple ps independently represents an integer from 0 to 4. In formula (33), each of the multiple rs independently represents an integer from 0 to 4, and each of the multiple s independently represents an integer from 0 to 3. In formula (34), each of the multiple ts independently represents an integer from 0 to 4. In formula (35), each of the multiple us independently represents an integer from 0 to 4, and each of the multiple vs independently represents an integer from 0 to 3. In formula (36), w represents an integer from 0 to 4, and x represents an integer from 0 to 2.

[0031] The amino compounds that can be used to synthesize o-quinone diazide compounds are compounds having one or more amino groups. The residues of the amino compound can be groups obtained by removing one or more hydrogen atoms from the amino group of the amino compound. Examples of amino compounds 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.

[0032] 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.

[0033] (D) Thermal crosslinking agent The thermal crosslinking agent of component (D) includes one or more compounds that crosslink the alkali-soluble resin by heat. The compounds constituting the thermal crosslinking agent may have multiple functional groups that can react with the alkali-soluble resin and bond to the polymerization chain of the alkali-soluble resin. Examples of such functional groups include alkoxy groups, epoxy groups, and oxazoline groups. The thermal crosslinking agent may also include alkoxy compounds having multiple alkoxy groups.

[0034] Alkoxy compounds that can be used as thermal crosslinking agents are thought to function primarily as thermal crosslinking agents that crosslink the polymerization chain of alkali-soluble resins through the reaction of an aromatic group (phenylene group) to which a phenolic hydroxyl group is bonded with an alkoxy group. The number of alkoxy groups in the alkoxy compound may be two or more, three or more, or four or more, and may be 20 or less, 15 or less, or 10 or less.

[0035] At least some of the two or more alkoxy groups in an alkoxy compound may be methoxy groups. In other words, an alkoxy compound may have multiple methoxy groups. An alkoxy compound may have four or more methoxy groups.

[0036] The alkoxy compound may have a cyclic group obtained by removing one or more hydrogen atoms from benzene, 1,3,5-triazine, glycoluryl, 2-imidazolidinone, or urea, and an alkoxyalkyl group (e.g., a methoxymethyl group, 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 hydrogen atoms from benzene may have a phenolic hydroxyl group bonded to the cyclic group. In this disclosure, compounds having an alkoxy group and a phenolic hydroxyl group may be considered as thermal crosslinking agents rather than alkali-soluble resins. Alkoxy compounds having an alkoxy group and a phenolic hydroxyl group may contribute to improving the sensitivity of photosensitive resin compositions.

[0037] The weight-average molecular weight of the alkoxy compound may be 3000 or less, 2000 or less, or 1500 or less, or 100 or more, from the viewpoint of balancing solubility in alkaline developer, photosensitive properties, and mechanical strength.

[0038] Specific examples of alkoxy compounds having a phenolic hydroxyl group include compounds represented by the following formulas (41), (42), (43), (44), (45), or (46). Specific examples of alkoxy compounds having a cyclic group obtained by removing one or more hydrogen atoms from 1,3,5-triazine, glycoluryl, 2-imidazolidinone, or urea include compounds represented by the following formulas (47), (48), (49), or (50).

[0039] In formulas (41) to (50), R ４０represents an alkoxyalkyl group, and multiple R in the same molecule ４０ They may be the same or different. ４０ This may be a methoxyalkyl group or a dimethoxyalkyl group, an example being a methoxymethyl group (-CH ２ OCH ３ ), and a 1,3-dimethoxypropan-2-yl group represented by the following formula.

[0040] The content of the thermal crosslinking agent (or alkoxy compound) may be 1 to 70% by mass, 2 to 50% by mass, or 3 to 40% by mass relative to the content of the alkali-soluble resin, from the viewpoint of heat resistance and warping suppression of the insulating resin film (cured film).

[0041] In the photosensitive resin composition, the total content of (A) alkali-soluble resin, (B) photoacid generator, and (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, or 100% by mass or less, based on the amount of the photosensitive resin composition. If the photosensitive resin composition contains a solvent, the amount of the photosensitive resin composition here refers to the amount excluding the solvent.

[0042] In addition to the components exemplified above, the photosensitive resin composition may further contain other components such as acrylic elastomers, adhesive aids, solvents, compounds that generate acid upon heating, dissolution accelerators, dissolution inhibitors, Cu rust inhibitors, coupling agents, surfactants, and leveling agents. The photosensitive resin composition may further contain alkali-soluble resins that do not fall under component (A), separate from component (A).

[0043] Acrylic elastomers are polymers containing one or more (meth)acrylic acid esters as monomer units. The (meth)acrylic acid ester may be an alkyl (meth)acrylic acid ester having an alkyl group which may have a substituent. "(meth)acrylic" means acrylic and methacrylic.

[0044] Acrylic elastomers contain one or more monomer units having a polyoxyalkylene group. The polyoxyalkylene group is represented by formula: -(OR ５１ )ｎ - A group that can be represented by, where R ５１ represents an alkylene group and n represents an integer of 2 or more. R ５１ may be an alkylene group having 2 to 5 carbon atoms. The repeating number n of the oxyalkylene group may be 10 or less, 5 or less, or 3 or less. Examples of the polyoxyalkylene group include a polyoxyethylene group (-(OCH ２ CH ２ )) ｎ -, and a polypropylene group (-(OCH(CH ３ ))CH ２ )) ｎ -. The monomer unit having a polyoxyalkylene group may be a group having no hydroxyl group, carboxy group, and amino group.

[0045] The monomer unit having a polyoxyalkylene group may be a monomer unit derived from a (meth)acrylate 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, R ５１ represents an alkylene group, R ５２ represents a hydrocarbon group, and n represents an integer of 2 or more. Examples of R ５１ are as described above. R ５２ may be an unsubstituted alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group), or an aryl group (e.g., phenyl group).

[0046] The acrylic elastomer may further contain a monomer unit other than the monomer unit having a polyoxyalkylene group. The proportion of the monomer unit 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 unit having a polyoxyalkylene group is within these ranges, particularly remarkable effects can be easily obtained in terms of reducing the turbidity of the photosensitive layer and having high mechanical strength and large elongation of the insulating resin film.

[0047] The acrylic elastomer may further contain monomer units having hydroxyl groups. The monomer units having hydroxyl groups may be groups that do not have polyoxyalkylene groups, carboxyl groups, or amino groups. The monomer units having hydroxyl groups may be monomer units derived from (meth)acrylic acid esters having hydroxyalkyl groups, or (meth)acrylamides having hydroxyalkyl groups, and examples of such include those represented by the following formula (52). In formula (52), R ５０ Z represents a hydrogen atom or a methyl group. ２ is -O- or -NH-, R ５３ R indicates an alkylene group. ５３ The group may be an alkylene group having 1 to 20, 1 to 10, or 1 to 4 carbon atoms, and examples include the ethane-1,2-diyl group and the 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, or 20 mol% or less, 15 mol% or less, or 10 mol% or less, based on the total monomer units contained in the acrylic elastomer.

[0048] The acrylic elastomer may further contain monomer units having a carboxyl group. The monomer units having a carboxyl group may be groups that do not have a polyoxyalkylene group, a hydroxyl group, or an amino group. The monomer units having a carboxyl group may also be monomer units derived from (meth)acrylic acid esters having a carboxyl group, and examples of such include those represented by the following formulas (53A) or (53B). In formulas (53A) and (53B), R ５０ R represents a hydrogen atom or a methyl group. In formula (53B), R ５４ R indicates an alkylene group. ５４The group may be an alkylene group having 1 to 20, 1 to 10, or 1 to 4 carbon atoms, and an example of such a group is an ethane-1,2-diyl group. The proportion of monomer units having a carboxyl group in the acrylic elastomer may be 3 mol% or more, 5 mol% or more, or 10 mol% or more, or 30 mol% or less, 25 mol% or less, or 20 mol% or less, based on the total monomer units contained in the acrylic elastomer.

[0049] The acrylic elastomer may further contain monomer units having an amino group. The monomer units having an amino group may be groups that do not have a polyoxyalkylene group, a hydroxyl group, or a carboxyl group. The monomer units having an amino group may be monomer units derived from (meth)acrylic acid esters having a secondary or tertiary amino group, and examples of such include those represented by the following formula (54). In formula (54), R ５０ R represents a hydrogen atom or a methyl group. ５５ R represents a hydrogen atom or an alkyl group. ５６ , R ５７ , R ５８ and R ５９ Each of these independently represents an alkyl group. ５５ R may be an alkyl group having 1 to 20, 1 to 10, or 1 to 5 carbon atoms (for example, a methyl group). ５６ , R ５７ , R ５８ and R ５９ The C1-C20, C1-C10, or C1-C5 alkyl group (e.g., a methyl group) may also be an alkyl group. The proportion of 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, or 20 mol% or less, 15 mol% or less, or 10 mol% or less, based on the total monomer units contained in the acrylic elastomer.

[0050] The acrylic elastomer may further contain monomer units having an unsubstituted alkyl group. The monomer units having an unsubstituted alkyl group may be monomer units derived from (meth)acrylic acid esters having an unsubstituted alkyl group, and an example thereof is represented by the following formula (55). In formula (55), R５０ R represents a hydrogen atom or a methyl group. ６０ R represents an unsubstituted alkyl group having 4 to 20 carbon atoms. ６０ Examples include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (or lauryl group), tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.

[0051] The acrylic elastomer may be a copolymer comprising monomer units having a polyoxyalkylene group and lacking hydroxyl, carboxyl, and amino groups; monomer units having a hydroxyl group and lacking a polyoxyalkylene group, carboxyl, and amino group; monomer units having a carboxyl group and lacking a polyoxyalkylene group, hydroxyl, and amino group; and monomer units having an amino group and lacking a polyoxyalkylene group, hydroxyl, and carboxyl group. The acrylic elastomer may also be a copolymer consisting only of monomer units having a polyoxyalkylene group, monomer units having a hydroxyl group, monomer units having a carboxyl group, and monomer units having an amino group, or it may be a copolymer consisting only of these monomer units and the remainder of unsubstituted alkyl group monomer units.

[0052] The acrylic elastomer content may be 0.5% by mass or more and 50% by mass or less relative to the alkali-soluble resin content. The acrylic elastomer content may be 1% by mass or more, or 2% by mass or more, relative to the alkali-soluble resin content, and may be 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.

[0053] The photosensitive resin composition may further contain other elastomers in addition to the acrylic elastomers exemplified above. These 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 monomer units having polyoxyalkylene groups. 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, relative to the content of the alkali-soluble resin.

[0054] The adhesive aid may contain nitrogen-containing aromatic compounds, examples of which include 1H-tetrazole, 5-aminotetrazole, 5-phenyltetrazole, and 5-methyltetrazole. The content of the adhesive aid may be 0 to 20% by mass, 0.01 to 20% by mass, 0.01 to 10% by mass, or 0.02 to 7% by mass relative to the content of the alkali-soluble resin of component (A).

[0055] Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methyl methoxypropionate, 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 individually 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.

[0056] Compounds that generate acid upon heating promote the thermal crosslinking reaction between the alkali-soluble resin and the oxazoline compound or alkoxy compound, which can further improve the heat resistance of the cured film. Compounds that generate acid upon heating can also contribute to improved resolution. Examples of compounds that generate acid upon heating include salts formed from strong acids such as onium salts and bases, and imidosulfonates. The content of the compound that generates 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).

[0057] The dissolution accelerator is a component that increases the dissolution rate of the exposed area in the developer solution and can contribute to improving sensitivity and resolution. The dissolution accelerator may contain compounds having a carboxyl group, a sulfo group, or a sulfonamide group. The content of the dissolution accelerator 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).

[0058] Dissolution inhibitors are compounds that inhibit the dissolution of the exposed area in an alkaline aqueous solution and are 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).

[0059] The coupling agent may include an organosilane compound (silane coupling agent), an aluminum chelate compound, or a combination thereof. Examples of commercially available organosilane compounds include KBM-403, KBM-803, and KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name). 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).

[0060] 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 (manufactured by DIC Corporation, trade name). The content of the surfactant or leveling agent may be 0 to 5% by mass, 0.001 to 5% by mass, or 0.01 to 3% by mass relative to the content of the alkali-soluble resin of component (A).

[0061] A method for forming an insulating resin film having a pattern can be formed by photolithography using the photosensitive resin composition according to this disclosure. Figure 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 Figure 1 includes a step S1 of forming a photosensitive layer containing the photosensitive resin composition, a step S2 of exposing a part of the photosensitive layer, a step S3 of developing to remove a part of the photosensitive layer to form an insulating resin film having a pattern including openings, and a step S4 of heating the insulating resin film.

[0062] The photosensitive layer containing the photosensitive resin composition can be, for example, a glass substrate, a semiconductor substrate, or a metal oxide insulator substrate (e.g., TiO ２ SiO ２ The photosensitive layer is formed on any substrate, such as a silicon nitride substrate. The photosensitive layer is formed, for example, by a method that includes applying a photosensitive resin composition containing a solvent onto 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.

[0063] A portion of the photosensitive layer is exposed by irradiation with an active light beam through a mask. The active light beam may be ultraviolet light, visible light, or radiation, and may be g-rays, h-rays, i-rays, or a combination thereof.

[0064] Developing removes a portion of the photosensitive layer, forming a resin film (insulating resin film) with a pattern including openings. A developer may be used for development. Examples of development using a developer include shower development, spray development, immersion development, and paddle development. The developed resin film (insulating resin film) may be washed with water or the like.

[0065] 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 also contain alcohol or a surfactant.

[0066] A portion of a 5 μm thick photosensitive layer containing a photosensitive resin composition, corresponding to a 5 μm wide through-hole, is exposed, and the exposed photosensitive layer is subjected to a 100 mJ / m³ test. ２ When developed under conditions in which through holes are formed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at the exposure dose, the thickness of the remaining photosensitive layer may be 95% or more of the thickness of the photosensitive layer before exposure.

[0067] By heating the resin film (insulating resin film), which is the photosensitive layer remaining after development, an insulating resin film is formed, which is a cured film containing a thermoset product of the photosensitive resin composition, mainly through a reaction between an alkali-soluble resin and a thermal crosslinking agent. The heating temperature may be 300°C or lower, 270°C or lower, or 250°C or lower, and may also be 160°C or higher. The heating time may be, for example, 0.5 hours or more and 5 hours or less.

[0068] The resin film (insulating resin film) can be heated using heating devices such as a quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace, microwave curing apparatus, and variable frequency microwave curing apparatus. The heating atmosphere may be, for example, an atmospheric atmosphere or an inert gas atmosphere containing nitrogen or the like.

[0069] The semiconductor device insulating resin film can be, for example, an insulating layer constituting the wiring portion of a semiconductor device. The semiconductor device may have a semiconductor chip, a conductive 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 containing a cured product of the photosensitive resin composition according to this disclosure.

[0070] Figure 2 is a partial cross-sectional view showing an example of a semiconductor device having an insulating layer. The semiconductor device 100 shown in Figure 2 has a semiconductor chip 10 and a wiring portion 20 provided on the semiconductor chip 10. The wiring portion 20 includes a conductor wiring layer 31 connected to the semiconductor chip 10, a surface protection layer 41, a cover coat layer 42, and conductive balls 50. The semiconductor device 100 may also be a semiconductor package having a wafer-level package (WLP) configuration. The surface protection layer 41 and the cover coat layer 42 are laminated in this order from the semiconductor chip 10 side, and the conductive balls 50 are provided outside the cover coat layer 42. The surface protection 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 this disclosure.

[0071] The semiconductor chip 10 has a chip body portion 11 having a circuit surface, a pad portion 12 provided on the circuit surface of the chip body portion 11, and a protective film 13 having a pattern including an opening that exposes the pad portion 12. The conductor wiring layer 31 of the wiring portion 20 is a rewiring layer connected to the pad portion 12 and extends between the surface protective layer 41 and the cover coat layer 42 to the inner portion of the conductive ball 50. A connection portion 32 for connecting to the conductive ball 50 is provided on the end of the conductor wiring layer 31. A barrier metal 33 is provided between the connection portion 32 and the conductive ball 50. The pad portion 12, conductor wiring layer 31, connection portion 32, barrier metal 33 and conductive ball 50 are electrically connected in this order.

[0072] The wiring portion (rewiring portion) of a semiconductor device may have multiple conductor wiring layers, and an insulating resin film containing a cured product of the photosensitive resin composition according to this disclosure may be provided as an interlayer insulating layer between adjacent conductor wiring layers. In a semiconductor device, the interlayer insulating layer, the surface protective layer, or both thereof may be an insulating resin film containing a cured product of the photosensitive resin composition according to this disclosure.

[0073] The semiconductor device may be a memory device. Examples of electronic devices including the semiconductor device described herein include mobile phones, smartphones, tablet devices, personal computers, and hard disk suspensions.

[0074] [Examples] The present invention is not limited to the following examples. 1. Raw materials (A) Alkali-soluble resin A1 Reaction product of imide compound ODPA / 1 represented by the following formula and 1,4-bismethoxymethylbenzene (PXDM) in the presence of p-toluenesulfonic acid (weight-average molecular weight: 36000)

[0075] A2 Reaction product of the imide compound BPPA / 1, represented by the following formula, and 1,4-bismethoxymethylbenzene (PXDM) in the presence of p-toluenesulfonic acid (weight-average molecular weight: 13000)

[0076] A3 3,4'-oxydiphthalic anhydride (α-ODPA, 1 equivalent) was dissolved in γ-butyrolactone. 2-amino-p-cresol (2 equivalents) was added, and the reaction mixture was stirred at room temperature for 1 hour. Subsequently, the reaction mixture was heated to 180°C and stirred for 4 hours to allow the imidation reaction to proceed, yielding the imide compound α-ODPA / 1. The imide compound α-ODPA / 1 and 1,4-bismethoxymethylbenzene (PXDM) were reacted in the presence of p-toluenesulfonic acid (PTS) at 180°C for 20 hours to obtain alkali-soluble resin A2 (weight-average molecular weight: 18000), which is a reaction product (novolac resin) of α-ODPA and PXDM.

[0077] A4 3,4'-biphthalic anhydride (α-BPDA, 1 equivalent) was dissolved in γ-butyrolactone. 2-amino-p-cresol (2 equivalents) was added, and the reaction mixture was stirred at room temperature for 1 hour. Subsequently, the reaction mixture was heated to 180°C and stirred for 4 hours to allow the imidation reaction to proceed, yielding the imide compound α-BPDA / 1. The imide compound α-BPDA / 1 and 1,4-bismethoxymethylbenzene (PXDM) were reacted in the presence of p-toluenesulfonic acid (PTS) at 180°C for 20 hours to obtain alkali-soluble resin A4 (weight-average molecular weight: 14000), which is a reaction product (novolac resin) of α-BPDA and PXDM.

[0078] (B) Photoacid Generator B1: 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane 1-naphthoquinone-2-diazide-5-sulfonic acid ester, esterification rate approximately 90%, manufactured by Daito Chemix Co., Ltd., trade name "PA28"

[0079] (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 A compound in which the group is a methoxymethyl group, manufactured by Honshu Chemical Industry Co., Ltd., trade name "HMOM-TPPA"

[0080] (D) Adhesion aid D1: 5-aminotetrazole (manufactured by Toyobo Co., Ltd., trade name "HAT")

[0081] (E) Silane coupling agent E1: 3-Glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM403")

[0082] 2. Each component of the photosensitive resin composition, according to the mixing ratio (parts by mass) shown in Table 1, was mixed with ethyl lactate (solvent). The mixture was pressure filtered through a polytetrafluoroethylene filter with 0.2 μm pores to obtain the photosensitive resin composition.

[0083]

[0084] 3. Evaluation 3-1. Photosensitive characteristics (1) Development time, residual film rate after development A photosensitive resin composition was applied to a silicon substrate by spin coating. The solvent was removed by heating the coating to form a photosensitive layer with a thickness of 10 μm. Next, using an i-line stepper (Canon Corporation, product name "FPA-3000iW"), the photosensitive layer was subjected to reduction projection exposure with the i-line (365 nm) through a mask having a pattern corresponding to through holes with a width of 5 μm. The i-line exposure dose was 600 mJ / cm². ２ The following was done. After exposure, a portion of the photosensitive layer was removed by developing with a 2.38% by mass TMAH aqueous solution until a square through-hole with sides of 5 μm was formed. The development time with the TMAH aqueous solution required to form the through-hole was recorded. The thickness of the remaining photosensitive layer, which is the insulating resin film, was measured, and the residual film percentage (%), which is the ratio of this value to the thickness of the photosensitive layer before exposure, was calculated.

[0085] (2) A resolution photosensitive resin composition was applied to a silicon substrate by spin coating. The solvent was removed by heating the coating to form a photosensitive layer with a thickness of 10 μm. Next, using an i-line stepper (Canon Corporation, product name "FPA-3000iW"), the photosensitive layer was reduced projection exposed to i-line (365 nm) light through a mask having a pattern corresponding to square through-holes of gradually different sizes ranging from 1 μm × 1 μm to 100 μm × 100 μm. The i-line exposure dose was 600 mJ / cm². ２ The following was observed. After exposure, a portion of the photosensitive layer was removed by developing with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The remaining photosensitive layer, an insulating resin film, was washed with water. The insulating resin film was observed, and the length of one side of the smallest formed through-hole was recorded as the resolution. A small resolution indicates good resolution.

[0086] 3-2. Thermal Properties (1) Glass Transition Temperature (Tg) of Cured Film A photosensitive resin composition was applied to a silicon substrate by spin coating, and the solvent was removed by heating the coating to form a photosensitive layer. The formed photosensitive layer was heated in an inert gas oven (INH-9CD-S) under a nitrogen atmosphere, raising the temperature to 230°C over 1 hour and maintaining it at 230°C for 2 hours to form a cured film (film thickness: approximately 10 μm). The glass transition temperature of the formed cured film was measured by thermomechanical analysis (TMA) under tensile mode, heating rate of 5°C / min, and load of 98 mN.

[0087] (2) Coefficient of linear expansion (CTE) of the cured film A photosensitive resin composition was applied to a silicon substrate by spin coating. The solvent was removed by heating the coating to form a photosensitive layer with a thickness of 12 μm. Next, the formed photosensitive layer was heated in an inert gas oven (INH-9CD-S) under a nitrogen atmosphere, raising the temperature to 230°C over 1 hour and maintaining it at 230°C for 2 hours to form a cured film (thickness: approximately 10 μm). A test piece with a width of 4 mm, a length of 30 mm, and a thickness of 10 μm was cut from the cured film. The dimensional change of the obtained test piece due to temperature change was measured using a thermomechanical analyzer in tensile mode, under atmospheric conditions, with the temperature raised from 30°C to 310°C at a rate of 5°C / min. From the measurement results, the coefficients of linear expansion (CTE) α1 and α2 of the test piece (cured film) were determined. α1 is a CTE in the temperature range below the glass transition region, and α2 is a CTE in the temperature range above the glass transition region.

[0088] (3) The 5% weight loss temperature photosensitive resin composition was applied to a silicon substrate by spin coating. The solvent was removed by heating the coating to form a photosensitive layer with a thickness of 12 μm. Next, the formed photosensitive layer was heated in an inert gas oven (INH-9CD-S) under a nitrogen atmosphere, raising the temperature to 230°C over 1 hour and maintaining it at 230°C for 2 hours to form a cured film (thickness: approximately 10 μm). A sample taken from the cured film was placed in an open-type sample container and heated to the 5% weight loss temperature (T) under the conditions of a nitrogen flow rate of 200 mL / min, a starting temperature of 30°C, and a heating rate of 10°C / min. ｄ５ ) was measured.

[0089] 3-3. Mechanical Properties (4) Elongation and Strength of Insulating Resin Film (Cured Film) A photosensitive resin composition was applied to a silicon substrate by spin coating. The solvent was removed by heating the coating to form a photosensitive layer with a thickness of 12 μm. Next, the formed photosensitive layer was heated in an inert gas oven (INH-9CD-S) under a nitrogen atmosphere, raising the temperature to 230°C over 1 hour and maintaining it at 230°C for 2 hours to form a cured film (thickness: approximately 10 μm). Strip-shaped test pieces with a width of 10 mm were prepared from the cured film peeled off the silicon substrate. Tensile tests of the test pieces were performed using an Autograph AGS-100NX manufactured by Shimadzu Corporation. In the tensile test, the distance between the chucks 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). Based on the tensile test results, the elongation at fracture and tensile strength of six test specimens obtained from cured films prepared under the same conditions were determined. The maximum values ​​of the elongation at fracture and tensile strength of the six test specimens are shown in Table 1.

[0090] 3-2. The results of the evaluation are shown in Table 1. The photosensitive resin composition of the example, which contains an alkali-soluble resin containing a constituent unit derived from the imide compound represented by formula (I), was confirmed to be able to form a pattern by developing it in a shorter time using an alkaline developer.

[0091] 10...Semiconductor chip, 11...Chip body, 12...Pad, 13...Protective film, 20...Wiring section, 31...Conductor wiring layer, 32...Connection section, 33...Barrier metal, 41...Surface protective layer (insulating layer), 42...Cover coat layer (insulating layer), 50...Conductive ball, 100...Semiconductor device.

Claims

1. (A) An alkali-soluble resin, (B) a photoacid generator which is a compound that generates an acid upon exposure to light, and (C) a thermal crosslinking agent which is a compound that crosslinks the alkali-soluble resin upon heating, and the alkali-soluble resin contains an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from an imide compound represented by the formula (I): having a polymer chain, and in the formula (I), X １ and X ２ are each independently a monovalent group represented by the formula (11) or (12): In the 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 at least one of R ２ or R ４ is a hydrogen atom. In the formula (12), R 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 at least one of R １ , R ３ and R ５ is a hydrogen atom. L is a covalent bond or a divalent organic group. R １０ is an alkyl group having 1 to 3 carbon atoms, and a plurality of R １０ in the same molecule may be the same or different, and m and n are each independently an integer of 0 to 3. A positive photosensitive resin composition.

2. L is a covalent bond, an oxy group, or formula (15) or (16): It is a divalent group represented by R ６ and R ７ The positive-type photosensitive resin composition according to claim 1, wherein each is independently a C1-C3 alkylene group, an arylene group which may be substituted with a C1-C3 alkyl group, or a group which comprises two or more arylene groups which may be substituted with a C1-C3 alkyl group and a covalent bond or C1-C3 alkylene group linking the two or more arylene groups.

3. The positive-type photosensitive resin composition according to claim 1, wherein the polymerization chain further comprises constituent units derived from a reactive compound selected from an aldehyde compound, a compound having a plurality of methoxymethyl groups, and a compound having a plurality of hydroxymethyl groups.

4. A method for forming an insulating resin film, comprising: exposing a portion of a photosensitive layer containing the positive-type photosensitive resin composition described in any one of claims 1 to 3; 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.

5. An insulating resin film comprising a cured product of a positive-type photosensitive resin composition according to any one of claims 1 to 3, and having a pattern including openings.

6. A semiconductor device comprising: a semiconductor chip; a wiring portion 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 an insulating resin film as described in claim 5.

7. Equation (I): It is expressed as follows, and in equation (I), X １ and X ２ These are independently given by equation (11) or (12): It is a monovalent group represented by formula (11), where R ２ , R ３ , R ４ and R ５ However, each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ２ or R ４ At least one of them is a hydrogen atom, and in formula (12), R １ , R ３ , R ４ and R ５ However, each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R １ , R ３ and R ５ At least one of them is a hydrogen atom, L is a covalent or divalent organic group, and R １０ However, it is an alkyl group having 1 to 3 carbon atoms, and multiple Rs in the same molecule １０ An imide compound in which m and n are independent integers from 0 to 3, and which may be the same or different.

8. L is a single bond, an oxy group, or formula (15) or (16): It is a divalent group represented by R ６ and R ７ The imide compound according to claim 7, wherein each is independently a C1-C3 alkylene group, an arylene group which may be substituted with a C1-C3 alkyl group, or a group which comprises two or more arylene groups which may be substituted with a C1-C3 alkyl group and a covalent bond or C1-C3 alkylene group linking the two or more arylene groups.

9. An alkali-soluble resin having a polymerization chain containing an imide-based structural unit which is a group obtained by removing one or more hydrogen atoms from the imide compound described in claim 7 or 8.

10. The alkali-soluble resin according to claim 9, wherein the polymerization chain further comprises constituent units derived from a reactive compound selected from an aldehyde compound, a compound having a plurality of methoxymethyl groups, and a compound having a plurality of hydroxymethyl groups.

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