Photosensitive resin composition, method for producing pattern cured film, cured film, interlayer insulating film, cover coat, surface protective film and electronic component

Abstract

A photosensitive resin composition comprises: (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a compound represented by the following formula (1), (C) a photopolymerization initiator, and (D) a thermal free radical generator. (In the formula (1), A is a divalent organic group and does not contain an acryloyl group or a methacryloyl group. R 1 ~R 4 Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. n1 and n2 are each independently an integer of 1 to 20. m1 and m2 are each independently 0 or 1. ).

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, a cured film, an interlayer insulating film, a cover coat, a surface protective film and an electronic component. Background Art

[0002] Conventionally, surface protective films and interlayer insulating films of semiconductor elements have been made of polyimide and polyphenylene terephthalate, which have excellent heat resistance, electrical properties, and mechanical properties. In recent years, photosensitive resin compositions having photosensitivity imparted to these resins themselves have been used. Use of such photosensitive resin compositions can simplify the production process of a patterned cured film and shorten the complicated production process (for example, see Patent Document 1).

[0003] However, in recent years, miniaturization of transistors that support the high performance of computers has reached the limit of the scaling law, and in order to further increase performance and speed, a stacked device structure in which semiconductor elements are stacked three-dimensionally has attracted attention.

[0004] In the stacked device structure, multi-die fan-out wafer level packaging (Multi-die Fanout Wafer Level Packaging) is a package manufactured by sealing multiple chips together in one package. Compared with the previously proposed fan-out wafer level packaging (manufactured by sealing one chip in one package), it can be expected to be low-cost and high-performance, so it has attracted much attention.

[0005] In the production of multi-chip fan-out wafer-level packaging, from the perspective of protecting high-performance chips, protecting sealing materials with low heat resistance, and improving yield, low-temperature curing properties, such as 200° C. or less, are strongly required (for example, see Patent Document 2). However, in the curing reaction at 200° C. or less, there is a problem that the polyimide precursor is not sufficiently imidized.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2009-265520

[0009] Patent Document 2: International Publication No. 2008 / 111470 Summary of the invention

[0010] The present invention aims to provide a photosensitive resin composition that can achieve a high imidization ratio even when the curing reaction is carried out at 200° C. or less and can produce a cured film having excellent mechanical properties. In addition, a method for producing a patterned cured film using the photosensitive resin composition, a cured film, an interlayer insulating film or the like produced using the cured film, and an electronic component including the interlayer insulating film or the like are provided.

[0011] Generally, the polymerizable monomer (crosslinking agent) used in the photosensitive resin composition is expected to volatilize in the heat treatment process for curing after the pattern is formed by the crosslinking reaction by exposure. However, when curing at a low temperature of 200°C or less, the crosslinking agent sometimes does not volatilize sufficiently and remains in the film, and it is believed that such a crosslinking agent may hinder the imidization of the polyimide precursor.

[0012] The present inventors have searched for a method of effectively utilizing the residual crosslinking agent to increase the imidization rate and have found that this object can be achieved by using a substance having a specific structure as a crosslinking agent and further using a thermal radical generator that promotes crosslinking during the curing reaction, thereby completing the present invention.

[0013] According to the present invention, the following photosensitive resin composition and the like can be provided.

[0014] 1. A photosensitive resin composition comprising:

[0015] (A) a polyimide precursor having a polymerizable unsaturated bond,

[0016] (B) a compound represented by the following formula (1),

[0017] (C) a photopolymerization initiator, and

[0018] (D) Thermal free radical generator.

[0019] [Chemistry 1]

[0020]

[0021] (In formula (1), A is a divalent organic group and does not contain an acryloyl group or a methacryloyl group. R 1 ~R 4 Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. n1 and n2 are each independently an integer of 1 to 20. m1 and m2 are each independently 0 or 1.

[0022] 2. The photosensitive resin composition according to 1, wherein n1 and n2 in the formula (1) are each independently 1 or 2.

[0023] 3. The photosensitive resin composition according to 1 or 2, wherein R in the above formula (1)1 and R 2 A hydrogen atom.

[0024] 4. The photosensitive resin composition according to any one of 1 to 3, wherein R in the above formula (1) 3 and R 4 A hydrogen atom.

[0025] 5. The photosensitive resin composition according to any one of 1 to 4, wherein A in the formula (1) is a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, an oxygen atom (—O—), or a group formed by linking two or more of these.

[0026] 6. The photosensitive resin composition according to any one of 1 to 5, wherein the component (D) is an organic peroxide.

[0027] 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (D) is a peroxyester or a dialkyl peroxide.

[0028] 8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (D) is a peroxyester.

[0029] 9. The photosensitive resin composition according to any one of 1 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).

[0030] [Chemistry 2]

[0031]

[0032] (In formula (11), X 1 is a tetravalent group having one or more aromatic groups. 1 is a divalent aromatic group. 11 and R 12 are each independently a hydrogen atom, a group represented by the following formula (12), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 11 and R 12 At least one of them is a group represented by the following formula (12). 11 The -COOR 12 The -CO- group and the -CO- group are in ortho positions with each other.)

[0033] [Chemistry 3]

[0034]

[0035] (In formula (12), R 13 ~R 15Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. m is an integer of 1 to 10.

[0036] 10. A method for producing a patterned cured film, comprising the following steps:

[0037] A step of applying the photosensitive resin composition according to any one of 1 to 9 onto a substrate and drying the composition to form a photosensitive resin film;

[0038] The process of pattern-exposing the photosensitive resin film to obtain a resin film;

[0039] A step of developing the pattern-exposed resin film using an organic solvent to obtain a patterned resin film; and

[0040] A step of heat-treating the patterned resin film.

[0041] 11. The method for producing a patterned cured film according to 10, wherein the temperature of the heat treatment is 200° C. or less.

[0042] 12. A cured film obtained by curing the photosensitive resin composition according to any one of 1 to 9.

[0043] 13. The cured film according to 12, which is a patterned cured film.

[0044] 14. An interlayer insulating film, a cover coat or a surface protective film produced using the cured film according to 12 or 13.

[0045] 15. An electronic component comprising the interlayer insulating film, cover coat or surface protection film according to 14.

[0046] According to the present invention, a photosensitive resin composition can be provided that can achieve a high imidization ratio even when the curing reaction is carried out at 200° C. or less and can produce a cured film having excellent mechanical properties. In addition, a method for producing a patterned cured film using the photosensitive resin composition, a cured film, an interlayer insulating film or the like produced using the cured film, and an electronic component including the interlayer insulating film or the like can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 It is a schematic diagram showing a manufacturing process of an electronic component according to one embodiment of the present invention. DETAILED DESCRIPTION

[0048] Hereinafter, embodiments of the photosensitive resin composition, method for producing a patterned cured film, cured film, interlayer insulating film, cover coat, surface protective film, and electronic component of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments.

[0049] In this specification, the term "A or B" may include either A or B, or both. In addition, the term "process" in this specification includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the desired effect of the process can be achieved.

[0050] The numerical range represented by "~" indicates a range including the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. In addition, regarding the content of each component in the composition in this specification, when there are multiple substances equivalent to each component in the composition, unless otherwise specified, it refers to the total amount of the multiple substances present in the composition. Furthermore, the exemplified materials may be used alone or in combination of two or more unless otherwise specified.

[0051] In this specification, "(meth)acrylate" means "acrylate" and "methacrylate".

[0052] [Photosensitive resin composition]

[0053] The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as "component (A)"), (B) a compound represented by formula (1) (hereinafter, also referred to as "component (B)"), (C) a photopolymerization initiator (hereinafter, also referred to as "component (C)"), and (D) a thermal radical generator (hereinafter, also referred to as "component (D)"). The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

[0054] The photosensitive resin composition of the present invention comprises a component (B) as a kind of polymerizable monomer and a component (D) that promotes crosslinking during the curing reaction, so during the curing reaction (heat treatment process), the components (B) are crosslinked (polymerized) with each other to form a crosslinked structure. Since the component (B) is a so-called bifunctional acrylate, and the functional group has a chain structure of a certain length or more, a long chain structure connected in a straight line can be formed by crosslinking them. This chain structure helps to improve the flexibility of the film. In addition, since there are few or no unreacted polymerizable monomers remaining, the imidization of the polyimide precursor can be promoted. Thus, a cured film with excellent mechanical properties, especially elongation at break, can be obtained.

[0055] In addition, the photosensitive resin composition of the present invention promotes the crosslinking reaction of the component (B) during the curing reaction, so the volatilization amount of the component is small. Therefore, when the cured film is formed, the film shrinkage is small and the dimensional accuracy is excellent.

[0056] Hereinafter, each component will be described.

[0057] (Component (A): polyimide precursor having a polymerizable unsaturated bond)

[0058] The component (A) is not particularly limited as long as it is a polyimide precursor having a polymerizable unsaturated bond, but preferably has a high transmittance when i-line is used as a light source for pattern formation and exhibits high cured film properties even when cured at a low temperature of 200° C. or less.

[0059] Examples of the polymerizable unsaturated bond include a double bond between carbon atoms.

[0060] The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (11). This has high i-line transmittance and can form a cured film having good physical properties even when cured at a low temperature of 200°C or less.

[0061] [Chemistry 4]

[0062]

[0063] (In formula (11), X 1 is a tetravalent group having one or more aromatic groups. 1 is a divalent aromatic group. 11 and R 12 are each independently a hydrogen atom, a group represented by the following formula (12), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 11 and R 12 At least one of them is a group represented by the following formula (12). 11 The -COOR 12 The -CO- group and the -CO- group are in ortho positions with each other.)

[0064] [Chemistry 5]

[0065]

[0066] (In formula (12), R 13 ~R 15 Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. m is an integer of 1 to 10 (preferably an integer of 2 to 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3).

[0067] X in formula (11) 1The tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups may be a tetravalent aromatic hydrocarbon group (having, for example, 6 to 20 carbon atoms) or a tetravalent aromatic heterocyclic group (having, for example, 5 to 20 atoms). 1 A tetravalent aromatic hydrocarbon group is preferred.

[0068] As X 1 Examples of the aromatic hydrocarbon group include a divalent to tetravalent (divalent, trivalent or tetravalent) group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and a divalent to tetravalent group formed from perylene.

[0069] As X 1 The tetravalent group having one or more aromatic groups may include, for example, a tetravalent group represented by the following formula, but is not limited thereto.

[0070] [Chemistry 6]

[0071]

[0072] (Where Z 1 and Z 2 Each is independently a divalent group or a single bond that is not conjugated with the benzene ring to which it is bonded. 3 It is an ether bond (-O-) or a thioether bond (-S-). )

[0073] Z 1 and Z 2 The divalent group is preferably -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group, or a difluoromethylene group, and more preferably -O-.

[0074] Z 3 Preferred is -O-.

[0075] Y in formula (11) 1 The divalent aromatic group may be a divalent aromatic hydrocarbon group (having, for example, 6 to 20 carbon atoms) or a divalent aromatic heterocyclic group (having, for example, 5 to 20 atoms). 1 A divalent aromatic hydrocarbon group is preferred.

[0076] As Y 1 The divalent aromatic hydrocarbon group may be, for example, a group represented by the following formula (13), but is not limited thereto.

[0077] [Chemistry 7]

[0078]

[0079] (In formula (13), R 21 ~R 28 Each is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.)

[0080] As R 21 ~R 28 It is a monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), preferably a methyl group.

[0081] R 21 ~R 28 The monovalent organic group having a halogen atom (preferably a fluorine atom) is preferably a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), and is preferably a trifluoromethyl group.

[0082] In formula (13), for example, R 22 and R 23 is a monovalent aliphatic hydrocarbon group (such as methyl), R 21 and R 24 ~R 28 A hydrogen atom.

[0083] As R in formula (11) 11 and R 12 The aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) includes methyl, ethyl, n-propyl, 2-propyl, n-butyl and the like.

[0084] In formula (11), R 11 and R 12 At least one of them is a group represented by formula (12), preferably R 11 and R 12 Both of them are groups represented by formula (12).

[0085] As R in formula (12) 13 ~R 15 The aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms includes methyl, ethyl, n-propyl, 2-propyl, etc. Preferably, it is methyl.

[0086] A polyimide precursor having a structural unit represented by formula (11) can be produced, for example, by reacting a tetracarboxylic dianhydride represented by the following formula (14) with a diamino compound represented by the following formula (15) in an organic solvent such as N-methylpyrrolidone to produce polyamic acid, adding a compound represented by the following formula (16), and reacting them in an organic solvent to introduce ester groups in whole or in part.

[0087] [Chemistry 8]

[0088]

[0089] H2N-Y 1 -NH2 (15)

[0090]

[0091] (In formula (14), X 1 is the X of formula (11) 1 In formula (15), Y 1 As defined in formula (11). In formula (16), R 13 ~R 15 and m are defined as in formula (12).

[0092] The tetracarboxylic dianhydride represented by the formula (14) and the diamino compound represented by the formula (15) may be used alone or in combination of two or more.

[0093] The content of the structural unit represented by formula (11) is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more relative to all structural units of component (A). The upper limit is not particularly limited and may be 100 mol%.

[0094] The component (A) may have a structural unit other than the structural unit represented by the formula (11). Examples of the structural unit other than the structural unit represented by the formula (11) include a structural unit represented by the following formula (17).

[0095] [Chemistry 9]

[0096]

[0097] (In formula (17), X 12 is a tetravalent group having one or more aromatic groups. 12 is a divalent aromatic group. 31 and R 32 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. 31 The -COOR 32 The -CO- group and the -CO- group are in ortho positions with each other.)

[0098] As X in formula (17) 12 The tetravalent group having one or more aromatic groups includes X of formula (11): 1 The same group as the tetravalent group having one or more aromatic groups. 12 The divalent aromatic group may be Y of formula (11): 1 As R 31 and R 32 The aliphatic hydrocarbon group having 1 to 4 carbon atoms includes the group consisting of 11 and R 12The same group as the aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0099] The content of structural units other than the structural unit represented by formula (11) is preferably less than 50 mol% based on all structural units of the component (A).

[0100] The structural units other than the structural unit represented by formula (11) may be used alone or in combination of two or more.

[0101] In the component (A), the ratio of esterified carboxyl groups in the groups represented by formula (12) is preferably 50 mol% or more, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%, relative to all carboxyl groups and all carboxylic acid esters in the polyimide precursor.

[0102] The molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in terms of number average molecular weight.

[0103] The number average molecular weight is measured by gel permeation chromatography (GPC) and calculated using a standard polystyrene calibration curve. Specific measurement conditions and the like are as described in the Examples.

[0104] (Component (B): a compound represented by formula (1))

[0105] The component (B) used in the present invention is a kind of polymerizable monomer, cross-linked with the component (A), or the components (B) are polymerized to form a cross-linked structure. Thus, a patterned resin film can be formed by photoreaction, and further, the cross-linking reaction is also promoted by the component (D) in the subsequent heat treatment reaction, thereby forming a long chain structure in which the components (B) are polymerized. As mentioned above, since the chain structure improves the flexibility of the film, it can also be said that the component (B) has the function of a plasticizer.

[0106] [Chemistry 10]

[0107]

[0108] (In formula (1), A is a divalent organic group and does not contain an acryloyl group or a methacryloyl group. R 1 ~R 4 Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. n1 and n2 are each independently an integer of 1 to 20. m1 and m2 are each independently 0 or 1.

[0109] When determining whether a certain compound is equivalent to the compound represented by formula (1), when there are multiple options for A, n1 and n2, if A, n1 and n2 can be selected in a manner that satisfies the compound represented by formula (1), it is considered to be equivalent to the compound represented by formula (1).

[0110] In formula (1), n1 and n2 are preferably integers of 1 to 10, more preferably integers of 1 to 5, and may be 1 or 2.

[0111] R 1 and R 2 It is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0112] R 3 and R 4 It is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0113] A may be a divalent organic group not containing an acryloyl group or a methacryloyl group, or a divalent organic group not containing a polymerizable unsaturated bond.

[0114] Examples of the divalent organic group of A include a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, an oxygen atom (—O—), or a group formed by connecting two or more (preferably 2, 3 or 4, more preferably 3 or 4) of these (for example, one or more (preferably 1 or 2) divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, one or more (preferably 1 or 2) divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and an oxygen atom (—O—)). Examples of the group formed by connecting include -(divalent aliphatic hydrocarbon group)-O-(divalent aliphatic hydrocarbon group)-, -(divalent aromatic hydrocarbon group)-(divalent aliphatic hydrocarbon group)-(divalent aromatic hydrocarbon group)-, and the like.

[0115] The number of carbon atoms in A is not particularly limited, and is, for example, 1 to 30, and preferably 1 to 20.

[0116] Examples of the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms (e.g., a divalent group corresponding to a methyl group, an ethyl group, or a propyl group) and a divalent cycloalkylene group having 3 to 20 carbon atoms (e.g., a divalent group derived from tricyclodecane).

[0117] Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group.

[0118] Specific examples of the component (B) include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxy-modified bisphenol A di(meth)acrylate, and propoxy-modified bisphenol A di(meth)acrylate.

[0119] The number of ethylene glycol chains in polyethylene glycol di(meth)acrylate is, for example, 5 to 20.

[0120] The number of propylene glycol chains in polypropylene glycol di(meth)acrylate is, for example, 5 to 20.

[0121] The ethoxy-modified compound is a compound in which an ethylene oxide chain is introduced into the molecule, and preferably contains 2 to 10 moles of the ethylene oxide chain per molecule.

[0122] The propoxy-modified compound is a compound having a propylene oxide chain introduced into the molecule, and preferably contains 2 to 10 moles of the propylene oxide chain per molecule.

[0123] The content of the component (B) is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the component (A).

[0124] ((B') component: other polymerizable monomers (cross-linking agents))

[0125] The photosensitive resin composition of the present invention may contain a crosslinking agent (component (B′)) other than the component (B).

[0126] Examples of the component include diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, triallyl isocyanurate, ethoxylated isocyanurate triacrylate, ethoxylated isocyanurate trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, and the like.

[0127] When using (B') component, content is preferably 0.1-15 mass parts with respect to 100 mass parts of (A) components, and more preferably 0.1-10 mass parts.

[0128] The photosensitive resin composition of the present invention may contain a crosslinking agent in an amount of, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or 100% by mass as the component (B).

[0129] (Component (C): photopolymerization initiator)

[0130] Preferred examples of the photopolymerization initiator of the component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzyl, benzyl dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; and 1-phenyl-1,2- Oxime esters such as diacetyl-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylacetone-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxyacetone-2-(O-benzoyl)oxime, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), and compounds represented by the following formula are preferred, but are not limited thereto. Oxime esters are preferred from the viewpoint of sensitivity.

[0131] [Chemistry 11]

[0132]

[0133] The content of component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 8 parts by mass relative to 100 parts by mass of component (A). Within the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical concavoconvex pattern is easily obtained.

[0134] ((D) ingredient: thermal radical generator)

[0135] Since the photosensitive resin composition of the present invention contains the (D) thermal radical generator, the cross-linking reaction between the (B) components is promoted in the heat treatment step.

[0136] As the component (D), an organic peroxide is preferred.

[0137] Examples of the organic peroxide include peroxyesters, dialkyl peroxides, ketone peroxides, peroxyketals, hydroperoxides, diacyl peroxides, and peroxydicarbonates, and peroxyesters and dialkyl peroxides are preferred.

[0138] The peroxyester is a compound represented by the following general formula.

[0139] R-(C=O)-OO-R' or

[0140] RO-(C=O)-OO-R'

[0141] In the formula, R and R' are each independently a substituted or unsubstituted alkyl group. Examples of the substituent include an aryl group having 6 to 10 carbon atoms. The alkyl group has, for example, 1 to 20 or 1 to 10 carbon atoms.

[0142] Specific examples of peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-hexyl peroxy-2-ethylhexanoate ... -tert-Butyl peroxyethylhexanoate, tert-Hexyl peroxyisopropyl monocarbonate, tert-Butyl peroxymaleic acid, tert-Butyl peroxy-3,5,5-trimethylhexanoate, tert-Butyl peroxylaurate, tert-Butyl peroxyisopropyl monocarbonate, tert-Butyl peroxy-2-ethylhexyl monocarbonate, tert-Hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-Butyl peroxyacetate, tert-Butyl peroxy-3-methylbenzoate, tert-Butyl peroxybenzoate, etc.

[0143] Examples of commercially available products include those with the trade names “Percumyl ND”, “PEROCTA ND”, “PERHEXYL ND”, “PERBUTYL ND”, “PERBUTYL NHP”, “PERHEXYL PV”, “PERBUTYL PV”, “PEROCTA O”, “PERHEXA 25O”, “PERHEXYL O”, “PERBUTYL O”, “PERHEXYL I”, “PERBUTYL MA”, “PERBUTYL 355”, “PERBUTYL L”, “PERBUTYL I-75”, “PERBUTYL E”, “PERHEXYL Z”, “PERHEXA 25Z”, “PERBUTYL A”, “PERBUTYL ZT”, and “PERBUTYL Z” (all manufactured by NOF Corporation).

[0144] The dialkyl peroxide is a compound represented by the following general formula.

[0145] ROO-R'

[0146] In the formula, R and R' are each independently a substituted or unsubstituted alkyl group. Examples of the substituent include an aryl group having 6 to 10 carbon atoms. The alkyl group has, for example, 1 to 20 or 1 to 10 carbon atoms.

[0147] Specific examples of the dialkyl peroxide include dicumyl peroxide, di-tert-butyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-hexyl peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3-yl.

[0148] Examples of commercially available products include "Percumyl D", "PERBUTYL P", "PERHEXA25B", "PERBUTYL C", "PERHEXYL D", "PERBUTYL D", "PERHEXYNE 25B", and "PERHEXYNE 25B-40" (all manufactured by NOF Corporation).

[0149] The component (D) is preferably a compound having a half-life temperature of 50°C or higher and 200°C or lower in one hour. From the viewpoint of promoting the polymerization reaction at a lower temperature, a compound having a half-life temperature of 50°C or higher and 175°C or lower in one hour is more preferred.

[0150] The one hour half-life temperature is determined as follows.

[0151] The organic peroxide was dissolved in benzene to prepare a 0.1 mol / L solution, which was sealed in a nitrogen-purged glass tube. The solution was immersed in a thermostatic bath set to a predetermined temperature for thermal decomposition, and the relationship between time (t) and a / (ax) was plotted. k was obtained from the slope of the obtained straight line, and the half-life (t 1 / 2 ).

[0152] dx / dt=k(ax)

[0153] ln a / (ax)=kt

[0154] x=a / 2

[0155] kt 1 / 2 =ln2

[0156] x: amount of decomposed organic peroxide

[0157] k: decomposition rate constant

[0158] t: time

[0159] a: Initial concentration of organic peroxide

[0160] Since k is represented by the following formula, k is measured at several temperatures, the activation energy ΔE is obtained from the slope of the straight line obtained by plotting the relationship between lnk and 1 / T, and the frequency factor A is obtained from the y-intercept.

[0161] k=Aexp[-ΔE / RT]

[0162] lnk=lnA-ΔE / RT

[0163] A: Frequency factor (1 / h)

[0164] ΔE: Activation energy (J / mol)

[0165] R: Gas constant (8.314 J / mol·K)

[0166] T: absolute temperature (K)

[0167] Instead of lnk, draw lnt 1 / 2 The straight line obtained by the relationship of 1 / T to 1 / T can obtain the half-life of the organic peroxide at any temperature, and can obtain the decomposition temperature that obtains any half-life (1 hour).

[0168] The content of the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass, and even more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0169] (Component (E): solvent)

[0170] The photosensitive resin composition of the present invention generally contains a solvent.

[0171] Examples of the solvent include organic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropionamide (for example, "KJCMPA-100" manufactured by KJ Chemical Co., Ltd.), and N-dimethylmorpholine.

[0172] The content of the solvent is not particularly limited, but is generally 50 to 1000 parts by mass based on 100 parts by mass of the component (A).

[0173] (Other ingredients)

[0174] The photosensitive resin composition of the present invention may further contain a coupling agent (adhesion aid), a surfactant or a leveling agent, a sensitizer, a rust preventive, a polymerization inhibitor, and the like in addition to the above-mentioned components.

[0175] (Coupling agent)

[0176] The coupling agent usually reacts with the component (A) to crosslink during the heat treatment after development, or the coupling agent itself polymerizes during the heat treatment step. This can further improve the adhesion between the obtained cured film and the substrate.

[0177] As the coupling agent, a silane coupling agent is preferred.

[0178] Preferred silane coupling agents include compounds having a urea bond (—NH—CO—NH—). This can further improve adhesion to the substrate even when curing is performed at a low temperature of 200° C. or less.

[0179] From the viewpoint of excellent adhesiveness when cured at low temperature, a compound represented by the following formula (31) is more preferable.

[0180] [Chemistry 12]

[0181]

[0182] (In formula (31), R 51 and R 52 Each is independently an alkyl group having 1 to 5 carbon atoms. j is an integer of 1 to 10, and k is an integer of 1 to 3.

[0183] Specific examples of the compound represented by formula (31) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc., preferably 3-ureidopropyltriethoxysilane.

[0184] As the silane coupling agent, a silane coupling agent having a hydroxyl group or a glycidyl group can be used. If a silane coupling agent having a hydroxyl group or a glycidyl group is used in combination with a silane coupling agent having a urea bond in the molecule, the adhesion of the cured film to the substrate during low temperature curing can be further improved.

[0185] Examples of the silane coupling agent having a hydroxyl group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, and ethyldiphenylsilane. Alcohol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis(trihydroxysilyl)benzene, 1,4-bis(methyldihydroxysilyl)benzene, 1,4-bis(ethyldihydroxysilyl)benzene, 1,4-bis(propyldihydroxysilyl)benzene, 1,4-bis(butyldihydroxysilyl)benzene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(diethylhydroxysilyl)benzene, 1,4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, and the compound represented by the following formula (32). Among them, in order to further improve the adhesion to the substrate, the compound represented by formula (32) is particularly preferred.

[0186] [Chemistry 13]

[0187]

[0188] (In formula (32), R 53 is a monovalent organic group having a hydroxyl group or a glycidyl group, R 54 and R 55 Each is independently an alkyl group having 1 to 5 carbon atoms. o is an integer of 1 to 10, and p is an integer of 1 to 3.

[0189] Examples of the compound represented by formula (32) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, and 4-glycidoxybutyltriethoxysilane.

[0190] The silane coupling agent having a hydroxyl group or a glycidyl group preferably further includes a group having a nitrogen atom, and more preferably further has an amino group or an amide bond.

[0191] Examples of the silane coupling agent further having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, bis(2-glycidoxymethyl)-3-aminopropyltriethoxysilane, and bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane.

[0192] Examples of the silane coupling agent further having an amide bond include compounds represented by the following formula (33).

[0193] R 56 -(CH2) q -CO-NH-(CH2) r -Si(OR 57 )3 (33)

[0194] (In formula (33), R 56 is a hydroxyl group or a glycidyl group, q and r are each independently an integer of 1 to 3, R 57 is methyl, ethyl or propyl. )

[0195] When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (A).

[0196] (Surfactant or leveling agent)

[0197] By including a surfactant or a leveling agent, coating properties (for example, suppression of streaks (uneven film thickness)) and developability can be improved.

[0198] As surfactants or leveling agents, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. can be mentioned. As commercial products, trade names "MEGAFAX F171", "F173", "R-08" (all manufactured by DIC Corporation); trade names "FLUORAD FC430", "FC431" (all manufactured by 3M Japan Co., Ltd.); trade names "Organosiloxane Polymer (Organosiloxane Polymer) KP341", "KBM303", "KBM403", "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

[0199] When a surfactant or a leveling agent is contained, the content of the surfactant or the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the component (A).

[0200] (Inhibitor)

[0201] By containing a polymerization inhibitor, good storage stability can be ensured.

[0202] Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.

[0203] Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluoquinone, tannic acid, p-benzylaminophenol, and nitrosoamines.

[0204] When a polymerization inhibitor is contained, the content of the polymerization inhibitor is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and further preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the component (A), from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the obtained cured film.

[0205] (Other ingredients)

[0206] The photosensitive resin composition of the present invention may contain a sensitizer.

[0207] Examples of the sensitizer include 7-N,N-diethylaminocoumarin, 7-diethylamino-3-thenoylcoumarin, 3,3'-carbonylbis(7-N,N-diethylamino)coumarin, 3,3'-carbonylbis(7-N,N-dimethoxy)coumarin, 3-thienylcarbonyl-7-N,N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N,N-methoxycoumarin, and 3- (4'-methoxybenzoyl) coumarin, 3,3'-carbonylbis-5,7-(dimethoxy) coumarin, benzyl acetophenone, 4'-N,N-dimethylaminobenzylidene acetophenone, 4'-acetylaminobenzylidene-4-methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4'-bis(N-ethyl, N-methyl)benzophenone, 4,4'-bis-(diethylamino)benzophenone, etc.

[0208] When a sensitizer is contained, the amount is more preferably 0.1 to 3.0 parts by mass, and further preferably 0.1 to 1.0 parts by mass, based on 100 parts by mass of the (a) polyimide precursor.

[0209] The photosensitive resin composition of the present invention may contain a rust inhibitor from the viewpoint of further improving the rust resistance. Examples of the rust inhibitor include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole, benzotriazole, 5-methylbenzotriazole, carboxybenzotriazole, etc. These tetrazolyl and triazole compounds may also be water-soluble salts thereof.

[0210] When the rust inhibitor is contained, the content is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 4.0 parts by mass, based on 100 parts by mass of the component (a).

[0211] The photosensitive resin composition of the present invention may contain a stabilizer. As the stabilizer, a known compound such as 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide may be used.

[0212] When the stabilizer is contained, the content is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the component (a).

[0213] The photosensitive resin composition of the present invention is essentially composed of components (A) to (D) and one or more components selected from the group consisting of component (B'), a coupling agent (adhesion aid), a surfactant, a leveling agent, a sensitizer, a rust inhibitor and a polymerization inhibitor, except for a solvent, and may further contain inevitable impurities within a range that does not impair the effects of the present invention.

[0214] The photosensitive resin composition of the present invention may be composed of, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or 100% by mass, in addition to the solvent.

[0215] (A) to (D) ingredients,

[0216] (A) to (D) components and (B') component,

[0217] (A) to (D) components, and at least one selected from the group consisting of component (B'), a coupling agent (adhesion aid), a surfactant, a leveling agent, a sensitizer, a rust inhibitor, and a polymerization inhibitor, or

[0218] The composition comprises components (A) to (D), component (B'), and one or more components selected from the group consisting of a coupling agent (adhesion aid), a surfactant, a leveling agent, a sensitizer, a rust preventive, and a polymerization inhibitor.

[0219] [cured film]

[0220] The cured film of the present invention can be obtained by curing the above-mentioned photosensitive resin composition. The cured film of the present invention can be used as a patterned cured film or a non-patterned cured film. The film thickness of the cured film of the present invention is preferably 5 to 20 μm.

[0221] The cured film of the present invention contains the polyimide derived from the component (A) and the high molecular compound (polymer) having a chain structure derived from the component (B), as described above.

[0222] [Method for producing patterned cured film]

[0223] The method for producing a patterned cured film of the present invention comprises the following steps: applying the photosensitive resin composition on a substrate and drying it to form a photosensitive resin film; exposing the photosensitive resin film to a pattern to obtain a resin film; developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film; and heating the patterned resin film. Thus, a patterned cured film can be obtained.

[0224] The method for manufacturing a pattern cured film of the present invention uses the above-mentioned photosensitive resin composition of the present invention, and through the above-mentioned process, the cross-linking reaction of the (B) polymerizable monomer (cross-linking agent) can be promoted during the heat treatment process, and the (B) components are cross-linked with each other, or between the (A) component and the (B) component, and a high-order structure can be obtained. Thus, a pattern cured film with less infiltration of the liquid and high liquid resistance can be manufactured. In addition, since the volatilization amount of the (B) polymerizable monomer (cross-linking agent) during the heat treatment process is small, the film shrinks less and the dimensional accuracy is excellent.

[0225] The method for producing a non-patterned cured film includes, for example, a step of forming the above-mentioned photosensitive resin film and a step of performing a heat treatment, and may further include a step of performing an exposure.

[0226] Examples of the substrate include semiconductor substrates such as glass substrates and Si substrates (silicon wafers); metal oxide insulator substrates such as TiO2 substrates and SiO2 substrates; silicon nitride substrates, copper substrates, copper alloy substrates, and the like.

[0227] The coating method is not particularly limited, and the coating can be performed using a spin coater or the like.

[0228] Drying can be performed using a hot plate, an oven, or the like.

[0229] The drying temperature is preferably 90 to 150° C., and more preferably 90 to 120° C. in order to suppress the reaction between the component (A) and the component (B) from the viewpoint of ensuring the dissolution contrast.

[0230] The drying time is preferably 30 seconds to 5 minutes.

[0231] Drying may be performed two or more times.

[0232] Thereby, the photosensitive resin film which formed the said photosensitive resin composition into a film shape can be obtained.

[0233] The film thickness of the photosensitive resin film is preferably 1 to 100 μm, more preferably 3 to 50 μm, and further preferably 5 to 30 μm.

[0234] The pattern exposure is performed by, for example, exposing to a predetermined pattern through a photomask.

[0235] Examples of the active light to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, and i-rays are preferred.

[0236] As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper exposure machine, a scanning exposure machine, etc. can be used.

[0237] By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed portion is removed with a developer.

[0238] The organic solvent used as the developer may be a good solvent for the photosensitive resin film alone, or a good solvent and a poor solvent may be appropriately mixed and used.

[0239] Examples of the good solvent include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone.

[0240] Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0241] A surfactant may be added to the developer in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the developer.

[0242] The development time can be set to twice the time required for immersing the photosensitive resin film and dissolving it, for example.

[0243] The development time varies depending on the components (A) and (B) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0244] After development, the film may be washed with a rinse solution.

[0245] As the rinse liquid, distilled water, methanol, ethanol, isopropyl alcohol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in appropriate mixtures, and may be used in combination in stages.

[0246] By heat-treating the patterned resin film, a patterned cured film can be obtained. The polyimide precursor of the component (A) undergoes a dehydration ring-closure reaction in the heat treatment step, and a part or all of it becomes a polyimide.

[0247] The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, further preferably 200°C or lower or 150 to 200°C.

[0248] By being within the above range, damage to the substrate and the device can be minimized, devices can be produced with a high yield, and energy saving of the process can be achieved.

[0249] The time of the heat treatment is preferably 5 hours or less, more preferably 30 minutes to 3 hours. Within the above range, a crosslinking reaction or a dehydration ring-closure reaction can be sufficiently performed.

[0250] The atmosphere for the heat treatment may be air or an inert atmosphere such as nitrogen. However, a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the pattern resin film.

[0251] Examples of the apparatus used for the heat treatment include a quartz tube furnace, an oven, a hot plate, a rapid annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0252] [Interlayer insulation films, cover coats, surface protection films, electronic components]

[0253] The cured film of the present invention can be used as a passivation film, a buffer coating film, an interlayer insulating film, a cover coating film, a surface protective film, or the like.

[0254] By using one or more selected from the group consisting of the above-mentioned passivation film, buffer coating film, interlayer insulating film, cover coating film and surface protection film, it is possible to manufacture highly reliable semiconductor devices, multilayer wiring boards, various electronic components such as electronic devices, etc.

[0255] An example of a process for manufacturing a semiconductor device as an electronic component of the present invention will be described with reference to the drawings.

[0256] Figure 1 This is a diagram showing a manufacturing process of a semiconductor device having a multilayer wiring structure as an electronic component according to one embodiment of the present invention.

[0257] exist Figure 1 In the present invention, a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. Then, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0258] Next, a photosensitive resin layer 5 of a chlorinated rubber-based, phenol novolac-based or other resin is formed on the interlayer insulating film 4, and a window 6A is provided by a known photolithography technique so as to expose a predetermined portion of the interlayer insulating film 4.

[0259] The interlayer insulating film 4 exposed by the window 6A is selectively etched to form a window 6B.

[0260] Next, the photosensitive resin layer 5 is removed using an etching solution that does not corrode the first conductive layer 3 exposed from the window 6B but corrodes the photosensitive resin layer 5 .

[0261] Furthermore, the second conductor layer 7 is formed by using a known photolithography technique to be electrically connected to the first conductor layer 3 .

[0262] When forming a multilayer wiring structure of three or more layers, the above-mentioned steps can be repeated to form each layer.

[0263] Next, the above-mentioned photosensitive resin composition is used to open the window 6C by pattern exposure to form the surface protection film 8. The surface protection film 8 protects the second conductor layer 7 from external stress, α rays, etc., and the obtained semiconductor device has excellent reliability.

[0264] In the above examples, an interlayer insulating film can also be formed using the photosensitive resin composition of the present invention.

[0265] Example

[0266] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples. In addition, the present invention is not limited to the following Examples.

[0267] Synthesis Example 1 (Synthesis of Polymer A1)

[0268] 7.07 g of 3,3',4,4'-diphenylether tetracarboxylic acid dianhydride (ODPA), 0.831 g of 2-hydroxyethyl methacrylate (HEMA), and a catalytic amount of 1,4-diazabicyclo[2.2.2]octanetriethylenediamine were dissolved in 30 g of N-methyl-2-pyrrolidone (NMP), stirred at 45°C for 1 hour, and then cooled to 25°C. A solution obtained by dissolving 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) in NMP was added, and then stirred at 30°C for 4 hours, and then stirred at room temperature overnight to obtain polyamic acid. After 9.45 g of trifluoroacetic anhydride was dropped into the solution, it was stirred at 45°C for 3 hours, a catalytic amount of benzoquinone was added, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was further added, and stirred at 45°C for 20 hours. This reaction liquid was dropped into distilled water, and the precipitate was separated and collected by filtration, and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as polymer A1).

[0269] The number average molecular weight of polymer A1 was determined by gel permeation chromatography (GPC) under the following conditions by standard polystyrene conversion. The number average molecular weight of polymer A1 was 40,000. The number average molecular weight was measured using a solution containing 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] relative to 0.5 mg of polymer A1.

[0270] Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.

[0271] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0272] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0273] Measurement conditions: Column Gelpack GL-S300MDT-5×2

[0274] Eluent: THF / DMF = 1 / 1 (volume ratio)

[0275] LiBr(0.03mol / L), H3PO4(0.06mol / L)

[0276] Flow rate: 1.0 mL / min, detector: UV270 nm

[0277] Furthermore, NMR measurement was performed under the following conditions to calculate the esterification rate of polymer A1 (reaction rate of carboxyl groups derived from ODPA and HEMA). The esterification rate was 80 mol % relative to all carboxyl groups of the polyamic acid (the remaining 20 mol % were carboxyl groups).

[0278] Measurement equipment: AV400M manufactured by Bruker BioSpin

[0279] Magnetic field strength: 400MHz

[0280] Reference substance: Tetramethylsilane (TMS)

[0281] Solvent: dimethyl sulfoxide (DMSO)

[0282] The components used in the following examples and comparative examples are as follows.

[0283] (Component (A): polyimide precursor having a polymerizable unsaturated bond)

[0284] Polymer A1: Polymer A1 obtained in Synthesis Example 1

[0285] (Component (B): polymerizable monomer)

[0286] B1: "A-200" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tetraethylene glycol diacrylate, a compound represented by the following formula)

[0287] [Chemistry 14]

[0288]

[0289] B2: "FA-324A" (manufactured by Hitachi Chemical Co., Ltd., ethoxy-modified bisphenol A diacrylate, a compound represented by the following formula, m=2, n=2)

[0290] [Chemistry 15]

[0291]

[0292] B3: "TEGDMA" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., triethylene glycol dimethacrylate, a compound represented by the following formula)

[0293] [Chemistry 16]

[0294]

[0295] B4: "FA-324M" (manufactured by Hitachi Chemical Co., Ltd., ethoxy-modified bisphenol A dimethacrylate, a compound represented by the following formula, m=2, n=2, a compound represented by the following formula)

[0296] [Chemistry 17]

[0297]

[0298] B5: "FA-321A" (manufactured by Hitachi Chemical Co., Ltd., ethoxy-modified bisphenol A diacrylate, a compound represented by the following formula, m=5, n=5, a compound represented by the following formula)

[0299] [Chemistry 18]

[0300]

[0301] B6: "FA-321M" (manufactured by Hitachi Chemical Co., Ltd., ethoxy-modified bisphenol A dimethacrylate, a compound represented by the following formula, m=5, n=5, a compound represented by the following formula)

[0302] [Chemistry 19]

[0303]

[0304] B7: "A-400" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., polyethylene glycol diacrylate, a compound represented by the following formula)

[0305] [Chemistry 20]

[0306]

[0307] B8: "FAP-324A" (manufactured by Hitachi Chemical Co., Ltd., propoxy-modified bisphenol A diacrylate, a compound represented by the following formula, m=2, n=2, a compound represented by the following formula)

[0308] [Chemistry 21]

[0309]

[0310] ((B') component)

[0311] B'1: "A-DCP" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula)

[0312] [Chemistry 22]

[0313]

[0314] B'2: "ATM-4E" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated pentaerythritol tetraacrylate, a compound represented by the following formula)

[0315] [Chemistry 23]

[0316]

[0317] B'3: "M-140" (manufactured by Toagosei Co., Ltd., N-acryloyloxyethyl hexahydrophthalimide, a compound represented by the following formula)

[0318] [Chemistry 24]

[0319]

[0320] B'4: "DPE-6A" (manufactured by Kyoeisha Chemical Co., Ltd., dipentaerythritol hexaacrylate, a compound represented by the following formula)

[0321] [Chemistry 25]

[0322]

[0323] B'5: "M-215" (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified diacrylate, a compound represented by the following formula)

[0324] [Chemistry 26]

[0325]

[0326] In addition, the (B') component refers to a component different from the (B) component used in the present invention.

[0327] (Component (C): photopolymerization initiator)

[0328] C1: "IRGACURE OXE 02" (manufactured by BASF Japan Ltd., a compound represented by the following formula)

[0329] [Chemistry 27]

[0330]

[0331] C2: "G-1820 (PDO)" (manufactured by Lambson, a compound represented by the following formula)

[0332] [Chemistry 28]

[0333]

[0334] ((D) ingredient: thermal radical generator)

[0335] D1: "Percumyl D" (manufactured by NOF Corporation, dicumyl peroxide, a compound represented by the following formula, 1-hour half-life temperature 135.7°C)

[0336] [Chemistry 29]

[0337]

[0338] D2: "PERBUTYL Z" (manufactured by NOF Corporation, tert-butyl peroxybenzoate, a compound represented by the following formula, 1-hour half-life temperature 124.7°C)

[0339] [Chemistry 30]

[0340]

[0341] D3: "PERBUTYL O" (manufactured by NOF Corporation, tert-butyl peroxy-2-ethylhexanoate, a compound represented by the following formula, 1-hour half-life temperature 92.1°C)

[0342] [Chemistry 31]

[0343]

[0344] (Component (E): solvent)

[0345] E1: "KJCMPA-100" (manufactured by KJ Chemical Co., Ltd., a compound represented by the following formula)

[0346] [Chemistry 32]

[0347]

[0348] (Other ingredients: inhibitor)

[0349] "Taobn" (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide, manufactured by Hampford Research)

[0350] (Other ingredients: sensitizer)

[0351] “EMK” (manufactured by Aldrich, a compound represented by the following formula, where Et represents an ethyl group)

[0352] [Chemistry 33]

[0353]

[0354] (Other ingredients: adhesive additives)

[0355] "UCT-801" (3-ureidopropyltriethoxysilane, manufactured by United Chemical Technologies)

[0356] (Other ingredients: rust inhibitor)

[0357] “5ATz” (manufactured by Tokyo Chemical Industry Co., Ltd., trade name “5-amino-1H-tetrazole”, a compound represented by the following formula)

[0358] [Chemistry 34]

[0359]

[0360] (Other ingredients: thermal alkali generator)

[0361] “4HP” (manufactured by Tokyo Chemical Industry Co., Ltd., trade name “4-hydroxypyridine”, a compound represented by the following formula)

[0362] [Chemistry 35]

[0363]

[0364] Examples 1 to 12 and Comparative Examples 1 to 7

[0365] [Preparation of Photosensitive Resin Composition]

[0366] The photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 7 were prepared using the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component relative to 100 parts by mass of the component (A).

[0367] [Evaluation of Cured Film]

[0368] (Determination of Imidization Ratio 1)

[0369] The obtained photosensitive resin composition was spin-coated on a silicon substrate (support substrate), dried at 105°C for 2 minutes, and further dried at 115°C for 2 minutes to form a resin film (A) having a film thickness of 12 μm after drying. The resin film was subjected to a 700 mJ / cm 2 Then, the wafer with the resin film was heated at 160°C for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace "μ-TF" (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured film (B). In addition, the wafer with the resin film obtained in the same manner as above was heated at 375°C for 2 hours to obtain a cured film (C).

[0370] The infrared absorption spectra of the resin film (A), the cured film (B), and the cured film (C) were measured to determine the infrared absorption spectra at 1370 cm -1 The absorbance of the peak caused by the CN stretching vibration of the imide group in the vicinity. The infrared absorption spectrum was measured using "IRAffinity-1s" (manufactured by Shimadzu Corporation) as a measuring device. The imidization rate of the resin film (A) was set to 0%, and the imidization rate of the cured film (C) was set to 100%, and the imidization rate of the cured film (B) was calculated by the following formula. The results are shown in Table 1 as "160°C" of the curing temperature.

[0371] Imidization ratio of resin film (B) = {(absorbance of resin film (B) - absorbance of cured film (A)) / (absorbance of coating film (C) - absorbance of cured film (A))} × 100

[0372] (Determination of Imidization Ratio 2)

[0373] A cured film was prepared in the same manner as in “Measurement 1 of Imidation Ratio” except that the curing temperature was changed to 180° C., and the imidation ratio was calculated. The results are shown in Table 1 with “180° C.” being the curing temperature.

[0374] (Determination of Imidization Ratio 3)

[0375] A cured film was prepared in the same manner as in "Measurement 1 of Imidation Ratio" except that the curing temperature was changed to 200°C, and the imidation ratio was calculated. The results are shown in Table 1 with "200°C" being the curing temperature.

[0376] (Evaluation of mechanical properties (elongation at break))

[0377] The photosensitive resin compositions obtained from Examples 2 and 3 and Comparative Examples 1 and 2 were respectively spin-coated on a silicon substrate, and dried by heating at 105°C for 2 minutes and at 115°C for 2 minutes on a hot plate to form a photosensitive resin film of about 12 μm. The obtained photosensitive resin film was subjected to wide band (BB) exposure using a "Mask Aligner MA-8" (manufactured by SUSS MicroTec), and the exposed resin film was developed using cyclopentanone to obtain a 10 mm wide strip-shaped patterned resin film. The obtained patterned wafer was heated at 160°C for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace "μ-TF" (manufactured by Koyo Thermo System Co., Ltd.) to obtain a patterned cured film of about 10 μm in thickness.

[0378] The obtained pattern cured film was immersed in a 4.9 mass % hydrofluoric acid aqueous solution and peeled off from the wafer. The peeled cured film was evaluated for elongation at break as follows. The elongation at break was measured using "Autograph AGS-100NH" (manufactured by Shimadzu Corporation) at a distance of 2 cm between the clamps and a tensile speed of 5 mm per minute. The results are shown in Table 2.

[0379] [Table 1]

[0380]

[0381] [Table 2]

[0382] Example 2 Example 3 Comparative Example 1 Comparative Example 2 Elongation at break (%) 61 80 45 40

[0383] As is apparent from Tables 1 and 2, the cured film obtained from the photosensitive resin composition of the present invention has a high imidization ratio of polyimide and is excellent in elongation at break.

[0384] Industrial Applicability

[0385] The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat, a surface protective film, and the like. The interlayer insulating film, the cover coat, or the surface protective film of the present invention can be used for electronic components, and the like.

[0386] Several embodiments and / or examples of the present invention have been described in detail above, but it is easy for those skilled in the art to make many changes to these illustrative embodiments and / or examples without substantially departing from the new teachings and effects of the present invention. Therefore, these many changes are included in the scope of the present invention.

[0387] The entire contents of the documents described in this specification and the application serving as the basis for the priority claim of the present application under the Paris Convention are incorporated herein by reference.

Claims

1. A photosensitive resin composition comprising: (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a compound represented by the following formula (1), (C) a photopolymerization initiator, and (D) a thermal free radical generator, [Chemistry 36] In formula (1), A is -(divalent aromatic hydrocarbon group)-(divalent aliphatic hydrocarbon group)-(divalent aromatic hydrocarbon group)-, does not contain an acryloyl group or a methacryloyl group, and R 1 ~R 4 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms; n1 and n2 each independently represent an integer of 1 to 20; and m1 and m2 each independently represent 0 or 1. 2 . The photosensitive resin composition according to claim 1 , wherein n1 and n2 in the formula (1) are each independently 1 or 2.

3. The photosensitive resin composition according to claim 1, wherein R in the formula (1) 1 and R 2 A hydrogen atom.

4. The photosensitive resin composition according to claim 1, wherein R in the formula (1) 3 and R 4 A hydrogen atom. 5 . The photosensitive resin composition according to claim 1 , wherein A in the formula (1) is —(a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms)-(a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms)-(a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms)-. The photosensitive resin composition according to claim 1 , wherein the component (D) is an organic peroxide. 7 . The photosensitive resin composition according to claim 1 , wherein the component (D) is a peroxyester or a dialkyl peroxide. 8 . The photosensitive resin composition according to claim 1 , wherein the component (D) is a peroxyester.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11): [Chemistry 37] In formula (11), X 1 is a tetravalent group having one or more aromatic groups, Y 1 is a divalent aromatic group, R 11 and R 12 are each independently a hydrogen atom, a group represented by the following formula (12), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 11 and R 12 At least one of them is a group represented by the following formula (12), -COOR 11 The -COOR 12 The -CO- group and the -CO- group are in the ortho position to each other. [Chemistry 38] In formula (12), R 13 ~R 15 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and m represents an integer of 1 to 10.

10. A method for producing a patterned cured film, comprising the following steps: A step of applying the photosensitive resin composition according to any one of claims 1 to 9 onto a substrate and drying the substrate to form a photosensitive resin film; The process of pattern-exposing the photosensitive resin film to obtain a resin film; The process of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film; as well as A step of heat-treating the patterned resin film. 11 . The method for producing a patterned cured film according to claim 10 , wherein the temperature of the heat treatment is 200° C. or less. 12 . A cured film obtained by curing the photosensitive resin composition according to claim 1 . The cured film according to claim 12 , which is a patterned cured film.

14. An interlayer insulating film, a cover coat or a surface protective film produced using the cured film according to claim 12 or 13. 15 . An electronic component comprising the interlayer insulating film, cover coat or surface protective film according to claim 14 .

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