Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor element and thermal base generator

Abstract

The present invention provides a photosensitive resin composition having excellent curability and storage stability. In addition, the present invention provides a cured film, a laminate, a method for manufacturing a cured film, and a semiconductor element using the above-mentioned photosensitive resin composition. The photosensitive resin composition contains a thermal base generator represented by formula (N1), and at least one precursor compound of a polyimide precursor and a polybenzoxazole precursor. In formula (N1), XN represents any one of a hydroxyl group, a carboxyl group, and a sulfonic acid group, ZN represents an oxygen atom or a sulfur atom, and LN is a hydrocarbon group connected from an adjacent nitrogen atom to XN, and represents a hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition containing at least one of a polyimide precursor and a polybenzoxazole precursor, a cured film, a laminate, a method for producing the cured film, and a semiconductor element. The present invention also relates to a thermal base generator. Background Art

[0002] The heat resistance and insulation properties of cyclized and cured resins such as polyimide resins and polybenzoxazole resins are excellent, and therefore they are suitable for various uses. The use is not particularly limited, but if the actual mounting semiconductor element is taken as an example, the use as a material or protective film of an insulating film or sealing material can be cited (refer to non-patent documents 1 and 2, etc.). In addition, it is also used as a base film or cover layer of a flexible substrate.

[0003] Such polyimide resins etc. are usually low in solubility to solvents. Therefore, often use the polymer precursor before the cyclization reaction, specifically, the method of being dissolved in the solvent with the state of a polyimide precursor or a polybenzoxazole precursor. Thus, it is possible to achieve excellent operability, and when manufacturing each product as described above, it is possible to be coated on substrates etc. and process in various forms. Then, heat and cyclize the polymer precursor, so as to form a cured resin. Except for the high performance possessed by polyimide resins etc., from the viewpoint of excellent adaptability in such manufacturing, it is increasingly expected that its application development in the industry.

[0004] There is a known technique for performing the cyclization of the polymer precursor as described above, using a base generator that generates a base by electromagnetic wave irradiation or heating. For example, Patent Document 1 describes a technique for performing the cyclization of the polymer precursor as described above using an ionic thermal base generator.

[0005] On the other hand, Patent Document 2 describes the use of a base generator having a urea bond as a polymerization initiator for polymerizing an epoxy group-containing compound.

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2013-139566

[0009] Patent Document 2: Japanese Patent Application Publication No. 2013-068681

[0010] Non-patent literature

[0011] Non-patent document 1: Science & Technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008

[0012] Non-patent literature 2: Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011 Summary of the invention

[0013] Technical issues to be solved by the invention

[0014] The ionic thermal base generator described in Patent Document 1 has a problem that the reactivity is relatively high and the storage stability of the photosensitive resin composition is low. In addition, the ionic base generator is easily activated at a common semiconductor process temperature (e.g., below 120° C.) in the previous process. As a result, there is also a problem that the base generation efficiency decreases in the process after cyclization of the polymer precursor, and the polymer precursor cannot be fully cured.

[0015] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition having excellent curability and storage stability.

[0016] Furthermore, the present invention aims to provide a cured film and a laminate formed using the above-mentioned photosensitive resin composition. Furthermore, the present invention aims to provide a method for producing a cured film using the above-mentioned photosensitive resin composition. Furthermore, the present invention aims to provide a semiconductor element including the above-mentioned cured film or the above-mentioned laminate.

[0017] Means for solving technical problems

[0018] The above-mentioned problems are solved by using a base generating agent having a specific structure. Specifically, the above-mentioned problems are solved by the following method <1>, preferably <2> to <23>.

[0019] <1>

[0020] A photosensitive resin composition comprising:

[0021] A thermal base generating agent represented by the following formula (N1), and

[0022] At least one precursor compound of a polyimide precursor and a polybenzoxazole precursor;

[0023] [Chemical formula 1]

[0024]

[0025] In formula (N1),

[0026] X N represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group,

[0027] Z N represents an oxygen atom or a sulfur atom,

[0028] RN1 and R N2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0029] L N From the adjacent nitrogen atom to X N and a trivalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

[0030] The * at both terminals independently represent a hydrogen atom or a monovalent organic group.

[0031] <2>

[0032] The photosensitive resin composition as described in <1>, wherein

[0033] In formula (N1), L N At least a part of the connecting chain in is a part of the arylene group.

[0034] <3>

[0035] The photosensitive resin composition as described in <1>, wherein

[0036] The thermal base generator is a compound represented by formula (N2);

[0037] [Chemical formula 2]

[0038]

[0039] In formula (N2),

[0040] X N1 and X N2 each independently represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group,

[0041] Z N1 represents an oxygen atom or a sulfur atom,

[0042] R N3 and R N4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0043] L N1 and L N2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms,

[0044] n1 represents 0 or 1,

[0045] n2 represents an integer from 0 to 10,

[0046] The sum of n1 and n2 is greater than 1,

[0047] n3 represents an integer greater than 1,

[0048] When n1=1, L N1 From the adjacent nitrogen atom to X N1 is a divalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain,

[0049] When n2≥1, L N2 From the adjacent nitrogen atom to X N2 The 1+n2-valent hydrocarbon group is a hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

[0050] <4>

[0051] The photosensitive resin composition as described in <3>, wherein

[0052] In formula (N2), X N1 and X N2 The total number and Z N1 The total number is equal.

[0053] <5>

[0054] The photosensitive resin composition as described in <3> or <4>, wherein

[0055] In formula (N2), L N1 and L N2 At least a part of the connecting chain in is a part of the arylene group.

[0056] <6>

[0057] The photosensitive resin composition as described in <1>, wherein

[0058] The thermal base generator is a polymer compound comprising a repeating unit represented by formula (N3);

[0059] [Chemical formula 3]

[0060]

[0061] In formula (N3),

[0062] X N3 represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group,

[0063] Z N2 represents an oxygen atom or a sulfur atom,

[0064] R N5 and R N6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0065] L N3 From the adjacent nitrogen atom to X N3It refers to a trivalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

[0066] <7>

[0067] The photosensitive resin composition as described in <6>, wherein

[0068] The thermal base generator is a polymer compound comprising a repeating unit represented by formula (N4);

[0069] [Chemical formula 4]

[0070]

[0071] In formula (N4),

[0072] X N4 each independently represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group,

[0073] With Z N2 Independently, Z N3 represents an oxygen atom or a sulfur atom,

[0074] With R N5 and R N6 Independently, R N7 and R N8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0075] L N4 From the adjacent nitrogen atom to X N4 and 2 to 6 hydrocarbon groups constituting the connecting chain,

[0076] L N5 It represents a divalent organic group.

[0077] <8>

[0078] The photosensitive resin composition as described in <6> or <7>, wherein

[0079] L N4 At least a part of the connecting chain in is a part of the arylene group.

[0080] <9>

[0081] The photosensitive resin composition according to any one of <1> to <8>, wherein

[0082] X in formula (N1) N , X in formula (N2) N1 or X N2 , X in formula (N3) N3 Or X in formula (N4) N4 It is a hydroxyl group or a carboxyl group.

[0083] <10>

[0084] The photosensitive resin composition according to any one of <1> to <9>, further comprising a photoradical polymerization initiator and a radical polymerizable compound.

[0085] <11>

[0086] The photosensitive resin composition according to any one of <1> to <10>, wherein

[0087] The precursor compound includes a polyimide precursor.

[0088] <12>

[0089] The photosensitive resin composition as described in <11>, wherein

[0090] The polyimide precursor has a structural unit represented by the following formula (1);

[0091] [Chemical formula 5]

[0092]

[0093] In formula (1), A 1 and A 2 Each independently represents an oxygen atom or NH, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group.

[0094] <13>

[0095] The photosensitive resin composition as described in <12>, wherein

[0096] R in formula (1) 113 and R 114 At least one of the compounds comprises a free radical polymerizable group.

[0097] <14>

[0098] The photosensitive resin composition according to any one of <1> to <13>, which is used for forming an interlayer insulating film for a redistribution layer.

[0099] <15>

[0100] A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <14>.

[0101] <16>

[0102] A laminate comprising two or more layers of the cured films according to <15>, and a metal layer between the cured films.

[0103] <17>

[0104] A method for producing a cured film, comprising a film forming step of applying the photosensitive resin composition described in any one of <1> to <14> to a substrate to form a film.

[0105] <18>

[0106] The method for producing a cured film according to <17>, comprising the step of heating the film at 50 to 450°C.

[0107] <19>

[0108] A semiconductor device comprising the cured film according to <15> or the laminate according to <16>.

[0109] <20>

[0110] A thermal base generator comprising a polymer compound comprising a repeating unit represented by formula (N3);

[0111] [Chemical formula 6]

[0112]

[0113] In formula (N3),

[0114] X N3 represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group,

[0115] Z N2 represents an oxygen atom or a sulfur atom,

[0116] R N5 and R N6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0117] L N3 From the adjacent nitrogen atom to X N3 It refers to a trivalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

[0118] <21>

[0119] The thermal base generating agent as described in <20>, wherein

[0120] The polymer compound comprises a repeating unit represented by formula (N4);

[0121] [Chemical formula 7]

[0122]

[0123] In formula (N4),

[0124] X N4 Each independently represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group,

[0125] With Z N2 Independently, Z N3 represents an oxygen atom or a sulfur atom,

[0126] With R N5 and R N6 Independently, R N7 and R N8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0127] L N4 From the adjacent nitrogen atom to X N4 and 2 to 6 hydrocarbon groups constituting the connecting chain,

[0128] L N5 It represents a divalent organic group.

[0129] <22>

[0130] The thermal base generating agent as described in <20> or <21>, wherein

[0131] L N4 At least a part of the connecting chain in is a part of the arylene group.

[0132] <23>

[0133] The thermal base generating agent according to any one of <20> to <22>, wherein

[0134] X N4 It is a hydroxyl group or a carboxyl group.

[0135] Effects of the Invention

[0136] According to the present invention, a photosensitive resin composition having excellent curability and storage stability can be obtained. In addition, by using the photosensitive resin composition of the present invention, a cured film, a laminate, a method for producing a cured film, and a semiconductor device of the present invention can be provided. DETAILED DESCRIPTION

[0137] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0138] In the present specification, a numerical range expressed by the symbol “to” indicates a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0139] The term "step" in this specification refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0140] Regarding the marking of the group (atomic group) in this specification, the marking without description of substitution and unsubstituted indicates that the group without substituent and the group with substituent are included at the same time. For example, when it is only recorded as "alkyl", it means that the alkyl without substituent (unsubstituted alkyl) and the alkyl with substituent (substituted alkyl) are included. In addition, when it is only recorded as "alkyl", it means that it can be chain or cyclic. In the case of chain, it means that it can be straight chain or branched. These meanings are also the same for "alkenyl", "alkylene" and "alkenylene".

[0141] Unless otherwise specified, "exposure" in this specification means not only drawing with light but also drawing with particle beams such as electron beams and ion beams. Examples of energy rays used for drawing include bright line spectrum of mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), and actinic rays such as X-rays, and particle beams such as electron beams and ion beams.

[0142] In this specification, “(meth)acrylate” means both or either of “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either of “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either of “acryloyl” and “methacryloyl”.

[0143] In the present specification, the concentration of the solid content in the composition is expressed as the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0144] In this specification, unless otherwise specified, physical property values ​​are values ​​under the conditions of a temperature of 23° C. and an atmospheric pressure of 101325 Pa (1 atmosphere).

[0145] In this specification, as long as there is no special description, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC determination), and are expressed as polystyrene conversion values. The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, using HLC-8220 (TOSOH CORPORATION system), and using guard columns HZ-L, TSKgelSuper HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (TOSOH CORPORATION system) as columns. And, as long as there is no special description, the solution measured using THF (tetrahydrofuran) is used as an eluent. And, as long as there is no special description, a wavelength 254nm detector of UV line (ultraviolet rays) is used in the detection in the GPC determination.

[0146] In this specification, when the positional relationship of each layer constituting the laminate is recorded as "up" or "down", other layers may exist on the upper side or lower side of the layer that becomes the reference in the multilayer concerned. That is, the layer that becomes the reference and the above-mentioned other layers may be further separated by the third layer or the third element, and the layer that becomes the reference and the above-mentioned other layers do not need to contact. In addition, unless otherwise specified, the direction of the stacked layers on the substrate is referred to as "up", or when there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of these up and down directions is for convenience in this specification. In actual practice, the "up" direction in this specification may also be different from the vertical direction.

[0147] [Photosensitive resin composition]

[0148] The photosensitive resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") contains at least one of a polyimide precursor and a polybenzoxazole precursor (hereinafter, also collectively referred to as "precursor containing a heterocyclic polymer"), and a specific thermal base generator described below. Furthermore, the photosensitive resin composition of the present invention preferably contains a photoradical polymerization initiator and a radical polymerizable compound. Hereinafter, each component contained in the photosensitive resin composition of the present invention is described in detail.

[0149] <Precursor of heterocyclic polymer>

[0150] In the present invention, the precursor of the heterocyclic ring-containing polymer may be a polyimide precursor or a polybenzoxazole precursor, and is more preferably a polyimide precursor.

[0151] <<Polyimide precursor>>

[0152] The polyimide precursor preferably contains a structural unit represented by the following formula (1). By setting such a structure, a composition having a more excellent film strength can be obtained.

[0153] [Chemical formula 8]

[0154]

[0155] A 1 and A 2 Each independently represents an oxygen atom or NH, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group.

[0156] A 1 and A 2 are each independently an oxygen atom or NH, preferably an oxygen atom.

[0157] <<<R 111 >>>

[0158] R 111 represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group comprising a combination thereof, preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group comprising a combination thereof, and more preferably an aromatic group having 6 to 20 carbon atoms.

[0159] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0160] Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group containing a combination thereof, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[0161] [Chemical formula 9]

[0162]

[0163] In the formula, A is preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHCO- and a combination of these; more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S- and -SO2-; further preferably a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -C(CF3)2- and -C(CH3)2-.

[0164] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine, p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminodiphenylamine. ,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoro propane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl- 4,4'-Diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate), 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis( 3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy) phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4 , at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaternary biphenyl. ,

[0165] Furthermore, diamines (DA-1) to (DA-18) shown below are also preferred.

[0166] [Chemical formula 10]

[0167]

[0168] Furthermore, as a preferred example, a diamine having at least two alkylene glycol units in the main chain can be cited. Preferably, the diamine contains two or more ethylene glycol chains or propylene glycol chains in total in one molecule, or both, and more preferably, the diamine contains no aromatic ring. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (these are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, but are not limited to these.

[0169] The structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176 are shown below.

[0170] [Chemical formula 11]

[0171]

[0172] In the above, x, y, and z are average values.

[0173] From the viewpoint of the flexibility of the obtained cured film, R 111 Preferably -Ar 0 -L 0 -Ar 0 - indicates. Among them, Ar 0 Each independently represents an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and is preferably a phenylene group. 0 represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHCO-, and a group selected from a combination thereof. The preferred range is the same as the meaning of A above.

[0174] From the perspective of i-ray transmittance, R 111A divalent organic group represented by the following formula (51) or formula (61) is preferred. In particular, a divalent organic group represented by formula (61) is more preferred from the viewpoint of i-ray transmittance and availability.

[0175] [Chemical formula 12]

[0176]

[0177] R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of the groups is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

[0178] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0179] [Chemical formula 13]

[0180]

[0181] R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

[0182] Examples of the diamine compound that imparts the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0183] <<<R 115 >>>

[0184] R in formula (1) 115 The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).

[0185] [Chemical formula 14]

[0186]

[0187] R 112 The meaning is the same as that of A, and the preferred range is also the same.

[0188] Regarding R in formula (1)115 The tetravalent organic group represented by is specifically a tetracarboxylic acid residue remaining after removing the acid dianhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[0189] [Chemical formula 15]

[0190]

[0191] R 115 represents a tetravalent organic group. 115 The meaning of is the same as R in formula (1) 115 same.

[0192] Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one of alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0193] Furthermore, as preferred examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned.

[0194] [Chemical formula 16]

[0195]

[0196] <<<R 113 and R 114>>>

[0197] R in formula (1) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. 113 and R 114 At least one of them contains a free radical polymerizable group, and more preferably both contain a free radical polymerizable group. As a free radical polymerizable group, it is a group that can undergo a crosslinking reaction through the action of a free radical, and as a preferred example, a group having an ethylenically unsaturated bond can be cited.

[0198] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryloyl group, and a group represented by the following formula (III).

[0199] [Chemical formula 17]

[0200]

[0201] In formula (III), R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferred.

[0202] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or a (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms; and the number of repetitions is preferably 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly)oxyalkylene group represents an oxyalkylene group or a polyoxyalkylene group.

[0203] Preferred R 201 Examples include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and -CH2CH(OH)CH2-, with ethylene, propylene, trimethylene, and -CH2CH(OH)CH2- being more preferred.

[0204] R is particularly preferred 200 is methyl, R 201 For ethylene.

[0205] As a preferred embodiment of the polyimide precursor in the present invention, R 113 or R 114The monovalent organic group may include aliphatic groups, aromatic groups, and aralkyl groups having 1, 2, or 3 acid groups, preferably 1 acid group. Specifically, it may include aromatic groups having 6 to 20 carbon atoms and aralkyl groups having 7 to 25 carbon atoms. More specifically, it may include phenyl groups having an acid group and benzyl groups having an acid group. The acid group is preferably a hydroxyl group. That is, R 113 or R 114 A group having a hydroxyl group is preferred.

[0206] As R 113 or R 114 The monovalent organic group represented by can preferably use a substituent that improves the solubility in a developer.

[0207] From the viewpoint of solubility in aqueous developer, R 113 or R 114 is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

[0208] From the viewpoint of solubility in organic solvents, R 113 or R 114 A monovalent organic group is preferred. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

[0209] The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more when cyclic). The alkyl group may be any of a straight chain, a branched chain, or a cyclic chain. As a straight chain or branched chain alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl can be mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl can be mentioned. As a polycyclic cyclic alkyl group, for example, adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, dicyclohexyl, and pinenyl can be mentioned. Furthermore, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group as described below is preferred.

[0210] The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenyl ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a substituted or unsubstituted aromatic heterocyclic group (a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthrine ring, a thianthracene ring, a chromene ring, a xanthene ring, a phenoxathiol ring, a phenothiazine ring or a phenazine ring).

[0211] Furthermore, the polyimide precursor preferably has fluorine atoms in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is practically 50% by mass or less.

[0212] Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by formula (1). Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0213] The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A) or (1-B).

[0214] [Chemical formula 18]

[0215]

[0216] A 11 and A 12 represents oxygen atom or NH, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of the groups preferably contains a radical polymerizable group, and more preferably a radical polymerizable group.

[0217] A 11 , A 12 , R 111 , R 113 and R 114 In the formula (1), A 1 , A 2 , R 111 , R 113 and R 114 The preferred range of has the same meaning.

[0218] R112 The preferred range of R in formula (5) 112 , and an oxygen atom is more preferred.

[0219] In formula (1-A), the bonding position of the benzene ring to the carbonyl group is preferably 4, 5, 3', or 4'. In formula (1-B), the bonding position is preferably 1, 2, 4, or 5.

[0220] In the polyimide precursor, the structural unit represented by formula (1) may be one or more. Furthermore, the structural isomers of the structural unit represented by formula (1) may be included. Furthermore, in addition to the structural unit of formula (1), the polyimide precursor may also include other types of structural units.

[0221] One embodiment of the polyimide precursor in the present invention is a polyimide precursor in which 50 mol % or more, further 70 mol % or more, and particularly 90 mol % or more of all structural units are structural units represented by formula (1). The upper limit is practically 100 mol % or less.

[0222] The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0223] The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0224] The polyimide precursor can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine, and is preferably obtained by halogenating dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the resulting mixture with diamine.

[0225] In the method for producing a polyimide precursor, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0226] The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

[0227] When producing a polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the solid can be precipitated by dissolving a polyimide precursor such as tetrahydrofuran in a soluble solvent.

[0228] <<Polybenzoxazole precursor>>

[0229] The polybenzoxazole precursor preferably includes a structural unit represented by the following formula (2).

[0230] [Chemical formula 19]

[0231]

[0232] R 121 Represents a divalent organic group, R 122 Represents a 4-valent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0233] R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14, and particularly preferably 6 to 12). 121 The aromatic group may be R of the above formula (1): 111 As the above-mentioned aliphatic group, a straight-chain aliphatic group is preferred. 121 Preferably it is derived from 4,4'-oxydibenzoyl chloride.

[0234] In formula (2), R 122 represents a tetravalent organic group. As a tetravalent organic group, R 115 R has the same meaning and the preferred range is also the same. 122 Preferably it is derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0235] R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group and has the same meaning as R in the above formula (1). 113 and R 114 The preferred ranges are the same.

[0236] In addition to the structural unit of the above formula (2), the polybenzoxazole precursor may further include other types of structural units.

[0237] The precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit from the viewpoint of being able to suppress the occurrence of warpage of the cured film due to ring closure.

[0238] [Chemical formula 20]

[0239]

[0240] Z has structure a and structure b, R 1sis a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R 2s is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, preferably structure a is 5 to 95 mol%, structure b is 95 to 5 mol%, and a+b is 100 mol%.

[0241] In formula (SL), preferred Z includes R in structure b. 5s and R 6s Z is a phenyl group. Furthermore, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by a commonly used gel permeation chromatography method. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be reduced, and the effects of suppressing warping and improving solubility can be achieved.

[0242] When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it is preferred to further contain a tetracarboxylic acid residue remaining after removing the dianhydride group from tetracarboxylic dianhydride as a structural unit in order to improve alkali solubility. Examples of these tetracarboxylic acid residues include R in the formula (1): 115 Example.

[0243] The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0244] The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0245] The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, further preferably 70% by mass or more, relative to the total solid content of the composition. Furthermore, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 95% by mass or less, further preferably 95% by mass or less, relative to the total solid content of the composition.

[0246] The photosensitive resin composition of the present invention may contain only one polymer precursor or two or more polymer precursors. When containing two or more polymer precursors, the total amount is preferably within the above range.

[0247] <Thermal alkali generator>

[0248] The thermal base generator of the present invention is represented by the following formula (N1): Hereinafter, this thermal base generator may be distinguished from other thermal base generators and referred to as a "specific thermal base generator".

[0249] [Chemical formula 21]

[0250]

[0251] In formula (N1), X N represents a nucleophilic group of any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, and Z N represents an oxygen atom (O) or a sulfur atom (S), R N1 and R N2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N From the adjacent nitrogen atom to X N The * at both ends independently represents a hydrogen atom or a monovalent organic group.

[0252] That is, the above-mentioned specific thermal base generating agent contains a urea bond (Z N =O, represents -NR N1 -C(=O)-NR N2 -bond. ) or thiourea bond (Z N =S, means -NR N1 -C(=S)-NR N2 -bond. ), and having these bonds and nucleophilic groups X N Hydrocarbon L N Hereinafter, these bonds are also collectively referred to as "urea-type bonds".

[0253] In this specification, regarding the hydrocarbon group L that connects the nitrogen atom and X, "connection chain" means the atomic chain between the adjacent nitrogen atoms and X, which connects these into the shortest atomic chain. When there are multiple Xs, the shortest atomic chain among them is regarded as the "connection chain". In addition, "X" is X N Or the following X N1 Also, regarding thermal alkali generating agents, "Z" is sometimes used as Z N Or the following Z N1 For example, in the exemplary compound BE-1 described below, L N It is composed of phenylene groups, the connecting chain is composed of 2 carbon atoms, and the number of atoms constituting the connecting chain (connecting chain length) is 2.

[0254] The above-mentioned specific thermal base generator is acidic, weakly acidic or neutral at room temperature, and does not promote the cyclization of the precursor of the heterocyclic polymer. Furthermore, the above-mentioned specific thermal base generator generates a base by heating, but has chemical stability and does not generate a base until about 120°C and even below 150°C, and is hardly deactivated as a base generator even after a normal semiconductor process. On the other hand, in the above-mentioned specific thermal base generator, for example, the nucleophilic effect of the nucleophilic group is activated by heating at a temperature of 150°C or above, so that, for example, as shown in the following reaction formula, the oxygen atom in the nucleophilic group bonds to the carbon atom in the urea-type bond, and a cyclization reaction rapidly proceeds in the molecule. As a result, the carbon atom located in the center of the urea-type bond bonds to the carbon atom that is not bonded to L. N Adjacent nitrogen atoms are rapidly dissociated, thereby efficiently generating amines (preferably secondary amines). Therefore, after heating, the cyclization of the heterocyclic polymer precursor is effectively performed by the base generated from the specific thermal base generator, so the obtained cured film has excellent elongation at break. In addition, the photosensitive resin composition of the present invention containing the above-mentioned specific thermal base generator is also excellent in storage stability due to the chemical stability of the specific thermal base generator as described above.

[0255] [Chemical formula 22]

[0256]

[0257] In the present invention, L N The number of carbon atoms in is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more, further preferably 5 or more, and particularly preferably 6 or more. From the viewpoint of allowing the above-mentioned intramolecular cyclization reaction to proceed rapidly, in the present invention, the above-mentioned linking chain length is more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0258] L NPreferably, the group includes a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a combination thereof, more preferably at least a cyclic alkylene group or an arylene group, and further preferably at least an arylene group. The cyclic alkylene group may be a single ring or a condensed ring. Furthermore, the cyclic alkylene group is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring, such as cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, etc. The arylene group may be a single ring or a condensed ring. Furthermore, the number of carbon atoms of the arylene group is preferably 6 to 14, more preferably 6 to 10, such as phenylene, naphthylene, anthracenediyl, phenanthrenediyl, biphenylene, triphenylene (terphenylene), etc., more preferably phenylene, naphthylene or biphenylene, etc. L N Can have in addition to X N The substituent T is the following substituent other than X. Furthermore, the substituent T may contain the same nucleophilic group as X (i.e., at least one of a hydroxyl group, a carboxyl group, and a sulfonic acid group). In the present invention, from the viewpoint of making the above-mentioned intramolecular cyclization reaction efficiently proceed, the number of such nucleophilic groups as a whole including X and the substituent T is preferably close to the total number of Z, more preferably within the range of ±2 of the total number of Z, further preferably within the range of ±1 of the total number of Z, and particularly preferably equal to the total number of Z. Furthermore, L N At least a part of the connecting chain in is preferably a part of an arylene group.

[0259] (Substituent T)

[0260] Examples of the substituent T include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt 1 、-CORt 1 、-COORt 1 、-OCORt 1 、-NRt 1 R 2 、-NHCORt 1 、-CONRt 1 R 2 、-NHCONRt 1 R 2 、-NHCOORt 1 、-SRt 1 、-SO2Rt 1 、-SO2ORt 1 、-NHSO2Rt 1 or -SO2NRt 1 R 2 . Rt 1 and Rt 2 Rt each independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. 1 and Rt 2 They may be bonded to form a ring.

[0261] As for the substituent T, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned. As a hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group can be mentioned. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, preferably a straight chain or a branched chain, and further preferably a branched chain. The number of carbon atoms of the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, preferably a straight chain or a branched chain. The number of carbon atoms of the alkynyl group is preferably 2 to 30, and further preferably 2 to 25. The alkynyl group may be any of a straight chain, a branched chain, and a cyclic group, preferably a straight chain or a branched chain. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the heterocyclic group are preferably nitrogen, oxygen or sulfur atoms. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.

[0262] The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in the substituent T above.

[0263] From the viewpoint of making the intramolecular cyclization reaction proceed rapidly, X N Preferably, the hydroxyl group or the carboxyl group is present, and more preferably the hydroxyl group. N The number of carbon atoms to which the two atoms are bonded is preferably the same as each other. Thus, the steric hindrance during the nucleophilic reaction is reduced, and the intramolecular cyclization reaction can be efficiently performed.

[0264] R N1 and R N2 Preferably, R is a hydrogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. N1 and R N2 When it is an aromatic hydrocarbon group, the number of carbon atoms is more preferably 6 to 18, and further preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl and naphthyl. N1 and R N2 When it is an aliphatic hydrocarbon group, the number of carbon atoms is more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. The aliphatic hydrocarbon group may be a linear or branched chain alkyl group, or a cyclic alkyl group. Examples of such aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, and cyclohexyl. The aromatic hydrocarbon group and the aliphatic hydrocarbon group may have a substituent T. R N1 and R N2 A hydrogen atom is particularly preferred.

[0265] The * parts at both ends are independently hydrogen atoms or monovalent organic groups. Regarding the * part, the monovalent organic group is preferably a hydrocarbon group consisting of one or more combinations of a group consisting of a linear or branched chain alkyl group, a cyclic alkyl group, a linear or branched chain alkenyl group, a cyclic alkenyl group, an alkyl group having an oxygen atom in the chain, and an aryl group. These can be linear or branched. As a monovalent organic group, the * part is preferably a cyclic alkyl group or an aryl group. In addition, regarding the * part, the monovalent organic group may contain heteroatom-containing bonds or substituents other than hydrocarbon groups. As such bonds, ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, etc. can be cited. In addition, as such substituents, hydroxyl groups, mercapto groups, cyano groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, nitro groups, carboxyl groups, acyl groups, acyloxy groups, sulfinic acid groups, sulfonic groups, alkyl ether groups, amino groups, etc. can be cited.

[0266] In the present invention, the compound represented by formula (N1) becomes a compound represented by formula (N1-a), formula (N2) to formula (N5) by having various structures as described above as monovalent organic groups at the * positions at both ends.

[0267] The compound represented by formula (N1) may be a low molecular compound or a high molecular compound. When the above compound is a low molecular compound, its molecular weight is preferably 50 to 1000. The upper limit is more preferably 800 or less, further preferably 600 or less, and particularly preferably 500 or less. The lower limit is more preferably 80 or more, further preferably 100 or more, and particularly preferably 120 or more. On the other hand, when the above compound is a high molecular compound, its molecular weight is preferably 2000 to 100000. The upper limit is more preferably 80000 or less, further preferably 60000 or less, and particularly preferably 40000 or less. The lower limit is more preferably 3000 or more, further preferably 5000 or more, and particularly preferably 7000 or more.

[0268] For example, the compound represented by the formula (N1) is preferably a compound represented by the formula (N1-a).

[0269] [Chemical formula 23]

[0270]

[0271] X in formula (N1-a) N , Z N , R N1 and R N2 With X in formula (N1) N , Z N , R N1 and R N2 Same. N1represents an arylene group, which may be a single ring or a condensed ring. The number of carbon atoms in the arylene group is preferably 6 to 14, more preferably 6 to 10, and examples thereof include phenylene, naphthylene, biphenylene, and the like. N2 represents an aryl group, which may be a single ring or a condensed ring. The number of carbon atoms of the aryl group is preferably 6 to 14, more preferably 6 to 10, and examples thereof include phenyl, naphthyl, biphenyl and the like.

[0272] Furthermore, as the monovalent organic group, a group having a structure in which the terminal * portion further has a urea-type bond and a nucleophilic group X are linked via a hydrocarbon group is preferred.

[0273] That is, in the present invention, the specific thermal base generator is preferably a compound represented by formula (N2).

[0274] [Chemical formula 24]

[0275]

[0276] In formula (N2), each bracket for n1, n2 or n3 is independent, and X N1 and X N2 Each independently represents a nucleophilic group of any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, and Z N1 represents an oxygen atom or a sulfur atom, R N3 and R N4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N1 and L N2 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, n1 represents 0 or 1, n2 represents an integer of 0 to 10, the sum of n1 and n2 is 1 or more, and n3 represents an integer of 1 or more. When n1=1, L N1 From the adjacent nitrogen atom to X N1 and n2≥1, L N2 From the adjacent nitrogen atom to X N2 The 1+n2-valent hydrocarbon group is a hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

[0277] With L in formula (N1) N Likewise, L N1 The group preferably includes a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a combination thereof, more preferably includes at least a cyclic alkylene group or an arylene group, and further preferably includes at least an arylene group. N1 Can have in addition to X N1 The above substituents other than T. and L N Similarly, the substituent T may contain the same nucleophilic group as X. N2It is also preferred to include a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a group of combinations thereof, more preferably at least a cyclic alkylene group or an arylene group, and further preferably at least an arylene group. Examples of cyclic alkylene groups include cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, etc. Examples of arylene groups include phenylene, naphthylene, anthracenediyl, phenanthrenediyl, etc., more preferably phenylene or naphthylene. N2 Can have in addition to X N2 The above substituents other than T. and L N Similarly, the substituent T may contain the same nucleophilic group as X. N1 At least a portion of the connecting chain in is preferably a portion of an arylene group, L N2 At least a part of the connecting chain in is preferably a part of an arylene group.

[0278] Respectively with X in formula (N1) N Likewise, X N1 and X N2 Preferably, hydroxyl or carboxyl is present, more preferably hydroxyl. n1 and n2 are the number of nucleophilic groups, and the total value of n1 and n2 is equal to Z. N1 The total number of the same degree of value, preferably X N1 and X N2 The total number and Z N1 That is, it is preferred that n1=1 and n2=0 for all brackets annotated with n3, n1=0 and n2=n3 for all brackets annotated with n3, and the sum of n1 and n2 for each bracket annotated with n3 is equal to n3. Therefore, n2 is preferably an integer of 0 to n3, and may also be the same value as n3. n3 is preferably 1 to 10, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 2 or 3. In this way, by making the number of atoms performing nucleophilicity and the number of atoms being nucleophilized the same, the steric hindrance during the nucleophilic reaction is reduced, and the intramolecular cyclization reaction can be carried out efficiently.

[0279] R N3 and R N4 Respectively with R in formula (N1) N1 and R N2 The meanings are the same, and preferably a hydrogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0280] The molecular weight of the compound represented by formula (N2) is preferably 100 to 2000. The upper limit is more preferably 1800 or less, further preferably 1500 or less, and particularly preferably 1200 or less. The lower limit is more preferably 120 or more, further preferably 150 or more, and particularly preferably 200 or more.

[0281] In the present invention, the specific thermal base generator is preferably a polymer compound containing a repeating unit represented by formula (N3). The thermal base generator of a polymer compound has the advantage of being less volatile.

[0282] [Chemical formula 25]

[0283]

[0284] In formula (N3), each repeating unit is independent, X N3 represents a nucleophilic group of any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, and Z N2 represents an oxygen atom or a sulfur atom, R N5 and R N6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N3 From the adjacent nitrogen atom to X N3 It refers to a trivalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

[0285] With L in formula (N1) N Likewise, L N3 Preferably, the group includes a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a combination thereof, more preferably includes at least a cyclic alkylene group or an arylene group, and further preferably includes at least an arylene group. Examples of the arylene group include phenylene, naphthylene, and biphenylene. N3 Can have in addition to X N3 Substituents other than T. N Similarly, the substituent T may contain the same nucleophilic group as X. N3 At least a part of the connecting chain in is preferably a part of an arylene group.

[0286] With X in formula (N1) N Likewise, X N3 Preferably, hydroxyl or carboxyl is used, and more preferably hydroxyl is used. N3 The total number and Z N2 By making the total number of atoms performing nucleophilicity and the number of atoms being nucleophilized equal, the steric hindrance during the nucleophilic reaction is reduced, and the intramolecular cyclization reaction can be carried out efficiently.

[0287] R N5 and R N6 Respectively with R in formula (N1) N1 and R N2 The meanings are the same, and preferably a hydrogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0288] Furthermore, the polymer compound containing a repeating unit represented by the formula (N3) is preferably a polymer compound containing a repeating unit represented by the formula (N4).

[0289] [Chemical formula 26]

[0290]

[0291] In formula (N4), each repeating unit is independent, X N4 Each independently represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, and Z N3 With Z N2 independently represent an oxygen atom or a sulfur atom, R N7 and R N8 With R N5 and R N6 independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N4 From the adjacent nitrogen atom to X N4 and L represents a tetravalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain. N5 represents a divalent organic group. In formula (N4), Z N2 , R N5 and R N6 With Z in formula (N3) N2 , R N5 and R N6 same.

[0292] With L in formula (N1) N Likewise, L N4 Preferably, the group includes a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a combination thereof, more preferably includes at least a cyclic alkylene group or an arylene group, and further preferably includes at least an arylene group. Examples of the arylene group include phenylene, naphthylene, and biphenylene. N4 Can have in addition to X N4 Substituents other than T. N Similarly, the substituent T may contain the same nucleophilic group as X. N4 At least a part of the connecting chain in is preferably a part of an arylene group.

[0293] L N5 Preferably, the hydrocarbon group is composed of one or a combination of two or more selected from the group consisting of linear or branched chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, and arylene groups. N5Preferably, the group includes a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a combination thereof, more preferably includes at least a cyclic alkylene group or an arylene group, and further preferably includes at least an arylene group. Examples of the arylene group include phenylene, naphthylene, and biphenylene. N5 It may have a substituent T.

[0294] With X in formula (N1) N Likewise, X N4 Preferably, hydroxyl or carboxyl is used, and more preferably hydroxyl is used. N4 The total number and Z N2 and Z N3 By making the total number of atoms performing nucleophilicity and the number of atoms being nucleophilized equal to each other, the steric hindrance during the nucleophilic reaction is reduced, and the intramolecular cyclization reaction can be carried out efficiently.

[0295] R N7 and R N8 Respectively with R in formula (N1) N1 and R N2 The meanings are the same, and preferably a hydrogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0296] The weight average molecular weight of the polymer compound represented by formula (N3) or (N4) is preferably 2000 to 100000. The upper limit is more preferably 8000 or less, further preferably 6000 or less, and particularly preferably 4000 or less. The lower limit is more preferably 3000 or more, further preferably 5000 or more, and particularly preferably 7000 or more.

[0297] The content of the thermal base generator of the polymer compound containing the repeating unit represented by formula (N3) or formula (N4) is preferably 0.01 to 30% by mass relative to the total solid content in the composition. The upper limit is more preferably 25% by mass or less, and further preferably 20% by mass or less. The lower limit is more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more.

[0298] The polymer compound including the repeating unit represented by the formula (N3) or the formula (N4) can be synthesized by, for example, polymerizing a dihydroxydiamine compound and a diisocyanate compound.

[0299] Furthermore, in the present invention, the specific thermal base generator is preferably a polymer compound containing a repeating unit represented by formula (N5).

[0300] [Chemical formula 27]

[0301]

[0302] In formula (N5), each repeating unit is independent, X N5represents a nucleophilic group of any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, and Z N4 represents an oxygen atom or a sulfur atom, R N9 and R N10 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N6 From the adjacent nitrogen atom to X N5 and L represents a divalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain. N7 It represents a divalent organic group.

[0303] With L in formula (N1) N Likewise, L N6 The group preferably includes a linear or branched alkylene group, a cyclic alkylene group or an arylene group, and a combination thereof, more preferably includes at least a cyclic alkylene group or an arylene group, and further preferably includes at least an arylene group. N6 Can have in addition to X N5 Substituents other than T. N Similarly, the substituent T may contain the same nucleophilic group as X. N6 At least a portion of the connecting chain in is preferably a portion of an arylene group. N7 Preferably, the hydrocarbon group is composed of one or a combination of two or more selected from the group consisting of linear or branched chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, and arylene groups. N7 More preferably, it is a cyclic alkylene group or arylene group having 5 to 10 carbon atoms. N7 It may have a substituent T.

[0304] With X in formula (N1) N Likewise, X N5 Preferably, hydroxyl or carboxyl is used, and more preferably hydroxyl is used. N5 The total number and Z N4 By making the total number of atoms performing nucleophilicity and the number of atoms being nucleophilized equal, the steric hindrance during the nucleophilic reaction is reduced, and the intramolecular cyclization reaction can be carried out efficiently.

[0305] R N9 and R N10 Respectively with R in formula (N1) N1 and R N2 The meanings are the same, and preferably a hydrogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0306] The weight average molecular weight of the polymer compound containing the repeating unit represented by formula (N5) is preferably 2000 to 100000. The upper limit is more preferably 80000 or less, further preferably 60000 or less, and particularly preferably 4000 or less. The lower limit is more preferably 5000 or more, further preferably 8000 or more, and particularly preferably 10000 or more.

[0307] The content of the thermal base generator of the polymer compound containing the repeating unit represented by formula (N5) is preferably 0.01 to 30% by mass relative to the total solid content in the composition. The upper limit is more preferably 25% by mass or less, and further preferably 20% by mass or less. The lower limit is more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more.

[0308] Examples of the thermal base generator represented by the formula (N1) include the following, but the present invention should not be construed in a limiting sense thereby.

[0309] [Chemical formula 28]

[0310]

[0311] [Chemical formula 29]

[0312]

[0313] [Chemical formula 30]

[0314]

[0315] Regarding the specific thermal base generator represented by the above formula (N1), the pKa of the conjugate acid of the generated base is preferably 8 or more, more preferably 9 or more, and further preferably 10 or more. The upper limit is not particularly limited, and is actually 14 or less. By setting the pKa of the specific thermal base generator to the above range, the generated base can efficiently carry out the cyclization reaction of the polymer precursor and can improve the elongation at break of the cured film at low temperature, and it is preferred from this point of view. The pKa here is set to a value determined by the following method.

[0316] The pKa described in this specification refers to the equilibrium constant Ka represented by the negative common logarithm pKa, taking into account the dissociation reaction of releasing hydrogen ions from the acid. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is set to a calculated value based on ACD / ChemSketch (registered trademark). Alternatively, the values ​​recorded in the "Revised 5th Edition of Chemistry Handbook Basics" compiled by the Chemical Society of Japan can be referred to.

[0317] The content of the specific thermal base generator is preferably 0.5 to 30% by mass relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0318] The content of the specific thermal base generator relative to 100 parts by mass of the polymer precursor is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, further preferably 1.5 parts by mass or more. For example, the upper limit is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.

[0319] By setting the content of the specific thermal base generator to be above the above lower limit, it is preferred to ensure good storage stability in the photosensitive resin composition and to achieve preferably mechanical properties of the cured film. By setting it to be below the above upper limit, it is preferred to ensure corrosion resistance of metals (for example, copper used for wiring, etc.).

[0320] The specific thermal base generating agent can be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

[0321] The photosensitive resin composition of the present invention may contain other thermal base generators other than the specific thermal base generator, or may not contain them. When other thermal base generators are contained, the photosensitive resin compositions described in WO2015 / 199219 and WO2015 / 199220 can be exemplified, and these contents are incorporated into this specification. In addition, in the present invention, it is also possible to have a configuration that substantially does not contain other thermal base generators other than the specific thermal base generator. Substantially not containing means that the content of the specific thermal base generator contained in the photosensitive resin composition of the present invention is less than 5% by mass, preferably less than 3% by mass, and more preferably 1% by mass.

[0322] <Photosensitive agent>

[0323] The photosensitive resin composition of the present invention preferably contains a photosensitizer. Examples of the photosensitizer include a photoradical polymerization initiator, and other than the photosensitive agent, for example, a photocuring accelerator, a thermal radical polymerization initiator, and a thermal acid generator may also be included.

[0324] <<Photopolymerization initiator>>

[0325] The photopolymerization initiator that can be used for the photosensitizer is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, it can be an activator that reacts with a photoexcited sensitizer to generate active free radicals.

[0326] The photo-radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Company) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0327] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azides, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. WO2015 / 199219, and the contents are incorporated into this specification.

[0328] Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, and the contents are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0329] As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can also be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can also be used.

[0330] As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE 2959, and IRGACURE 127 (product names: all manufactured by BASF) can be used.

[0331] As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

[0332] As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength that matches a light source having a wavelength of 365 nm or 405 nm, can also be used.

[0333] Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, commercially available products such as IRGACURE 819 and IRGACURE TPO (trade names: both manufactured by BASF Corporation) can be used.

[0334] Examples of the metallocene compound include IRGACURE 784 (manufactured by BASF Corporation) and the like.

[0335] As the photo-radical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, the exposure latitude (exposure margin) is relatively wide and they also function as a photocuring accelerator, so they are particularly preferred.

[0336] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.

[0337] Preferred oxime compounds include, for example, compounds of the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the photosensitive resin composition of the present invention, it is preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0338] [Chemical formula 31]

[0339]

[0340] Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, a photoradical polymerization initiator described in JP-A-2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

[0341] Oxime compounds having fluorine atoms can be used. Specific examples of these oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

[0342] As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in JP-A-2007-269779 or an oxime compound having a thioaryl group as disclosed in JP-A-2009-191061.

[0343] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0344] More preferred photoradical polymerization initiators are further preferably trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, and at least one compound selected from the group consisting of trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds, and it is further preferred to use metallocene compounds or oxime compounds, and it is further preferred to use oxime compounds.

[0345] In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, quinones formed by condensing an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, compounds represented by the following formula (I) may be used.

[0346] [Chemical formula 32]

[0347]

[0348] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, a phenyl group or a biphenyl group substituted by at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkyl group having 2 to 12 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by formula (II), or is I00 The same group, R I02 ~RI04 Each is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen group.

[0349] [Chemical formula 33]

[0350]

[0351] In the formula, R I05 ~R I07 R of the above formula (I) I02 ~R I04 same.

[0352] Furthermore, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

[0353] When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The photopolymerization initiator may contain only one or more. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0354] <<Thermal polymerization initiator>>

[0355] As the photosensitizer, a thermal polymerization initiator can be used, and in particular, a thermal free radical polymerization initiator can be used. The thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymer precursor can be cyclized and the polymerization reaction of the polymer precursor can be carried out, so that a higher degree of heat resistance can be achieved.

[0356] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

[0357] When a thermal free radical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 5 to 15% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The thermal free radical polymerization initiator may contain only one or more than one. When two or more thermal free radical polymerization initiators are contained, the total amount is preferably within the above range.

[0358] <Polymerizable compounds>

[0359] <<Free Radical Polymerization Compound>>

[0360] The photosensitive resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a free radical polymerizable compound can be used. The free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, groups having ethylenically unsaturated bonds such as vinyl, aryl, vinylphenyl, (meth)acryloyl, etc. can be cited. The free radical polymerizable group is preferably a (meth)acryloyl group.

[0361] The number of radical polymerizable groups possessed by the radical polymerizable compound may be 1 or 2 or more, preferably the radical polymerizable compound has 2 or more radical polymerizable groups, more preferably 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

[0362] The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

[0363] From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one free radical polymerizable compound having two or more functional groups, more preferably at least one free radical polymerizable compound having three or more functional groups. In addition, it may be a mixture of a free radical polymerizable compound having two or more functional groups and a free radical polymerizable compound having three or more functional groups. In addition, the number of functional groups of a free radical polymerizable compound indicates the number of free radical polymerizable groups in one molecule.

[0364] As specific examples of free radical polymerizable compounds, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, sulfanyl and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids can also be preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols and substitution reaction products of unsaturated carboxylic acid esters or amides with dissociable substituents such as halogenated groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Furthermore, as another example, the unsaturated carboxylic acid may be replaced by a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, etc. As a specific example, reference may be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein.

[0365] Furthermore, the radical polymerizable compound is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, and polyfunctional alcohols such as glycerol or trimethylolethane to which ethylene oxide or propylene oxide is added and then (meth)acrylated. Compounds, (meth) acrylic acid urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, polyester acrylates described in Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also suitable. In addition, polyfunctional (meth) acrylic esters obtained by reacting polyfunctional carboxylic acids with compounds having cyclic ether groups and ethylenically unsaturated bonds such as (meth) acrylic acid glycidyl esters can also be cited.

[0366] Furthermore, as preferred radical polymerizable compounds other than the above, compounds having a fluorene ring and having two or more groups containing ethylenically unsaturated bonds, or cardo resins described in JP-A-2010-160418, JP-A-2010-129825, and JP-4364216 may be used.

[0367] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 1-040337, Japanese Patent Publication No. 1-040336, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 2-025493 can also be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, compounds introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0368] In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. WO2015 / 199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

[0369] In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable compounds. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resultant.

[0370] Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated into the present specification.

[0371] As the radical polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which (meth)acryloyl groups of these are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0372] Examples of commercially available radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Company, Inc., SR-209, 231, and 239, a bifunctional methyl acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc., DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by NIPPON PAPERINDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0373] As the radical polymerizable compound, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 2-032293, Japanese Patent Publication No. 2-016765, and urethane compounds having an ethylene oxide skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 1-105238 can also be used.

[0374] The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. Among the radical polymerizable compounds having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. It is particularly preferred that among the free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. As commercially available products, for example, as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. can be cited.

[0375] The acid value of the radical polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radical polymerizable compound is within the above range, the production or handling properties are excellent, and the developability is excellent. In addition, the polymerizability is good.

[0376] From the viewpoint of suppressing the warping accompanying the elastic modulus control of the cured film, the photosensitive resin composition of the present invention can preferably use a monofunctional free radical polymerizable compound as a free radical polymerizable compound. As the monofunctional free radical polymerizable compound, preferably used are n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-hydroxymethyl (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid triallyl ester and other allyl compounds. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred in order to suppress volatilization before exposure.

[0377] <<Polymerizable compounds other than the above-mentioned radical polymerizable compounds>>

[0378] The photosensitive resin composition of the present invention may further contain polymerizable compounds other than the above-mentioned free radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned free radical polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

[0379] <<<Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group>>>

[0380] As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

[0381] [Chemical formula 34]

[0382]

[0383] In the formula, t represents an integer of 1 to 20, R 104 represents a t-valent organic group having 1 to 200 carbon atoms, R 105 Indicated by -OR 106 or-OCO-R 107 The group represented by R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R 107 It represents an organic group having 1 to 10 carbon atoms.

[0384] [Chemical formula 35]

[0385]

[0386] In the formula, R 404 represents a divalent organic group having 1 to 200 carbon atoms, R 405 Indicated by -OR 406 or-OCO-R 407 The group represented by R 406 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R 407 It represents an organic group having 1 to 10 carbon atoms.

[0387] [Chemical formula 36]

[0388]

[0389] In the formula, u represents an integer from 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, R 505 Indicated by -OR 506 or, -OCO-R 507 The group represented by R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R 507 It represents an organic group having 1 to 10 carbon atoms.

[0390] Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (these are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (these are trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol), etc.

[0391] Specific examples of the compound represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHIYUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, and NIKALAC MW-100LM (these are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0392] <<<Epoxy compound (compound having epoxy group)>>>

[0393] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction at 200°C or below, and since a dehydration reaction due to crosslinking does not occur, it is difficult to cause film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the composition can be effectively suppressed.

[0394] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and preferably the number of structural units is 2 to 15.

[0395] Examples of epoxy compounds include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, alkylene glycol epoxy resins such as propylene glycol diglycidyl ether, polyalkylene glycol epoxy resins such as polypropylene glycol diglycidyl ether, epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, etc. Specifically, there can be mentioned EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, and EPICLON (registered trademark) EXA-4822 (these are trade names, DIC Corporation), RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA Corporation), etc. Among these, epoxy resins containing polyethylene oxide groups are preferred from the perspective of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

[0396] <<<Oxetane compound (compound having an oxetane group)>>>

[0397] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As specific examples, ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[0398] <<<Benzoxazine compound (compound having a polybenzoxazolyl group)>>>

[0399] Benzoxazine compounds are preferred because they do not generate outgassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and further reduce thermal shrinkage to suppress the generation of warpage.

[0400] Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0401] When a polymerizable compound is contained, its content is preferably more than 0% by mass and less than 60% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably more than 5% by mass. The upper limit is more preferably less than 50% by mass, and further preferably less than 30% by mass.

[0402] The polymerizable compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount thereof is preferably within the above range.

[0403] <Solvent>

[0404] The photosensitive resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

[0405] Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, etc.) ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

[0406] As ethers, for example, preferred ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

[0407] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

[0408] As the aromatic hydrocarbons, for example, preferred aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.

[0409] As the sulfoxides, for example, dimethyl sulfoxide is preferred.

[0410] As the amides, preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and the like.

[0411] The solvent is preferably in the form of a mixture of two or more kinds from the viewpoint of improving the coating surface shape and the like.

[0412] In the present invention, preferably, a solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate or a mixed solvent consisting of two or more thereof is used. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously.

[0413] The content of the solvent is preferably set to an amount in which the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and further preferably 40 to 70% by mass from the viewpoint of coating properties. The content of the solvent can be adjusted according to the desired thickness and coating method.

[0414] The solvent may be contained in one kind or in two or more kinds. When two or more kinds of solvents are contained, it is preferred that the total amount thereof is within the above range.

[0415] <Migration inhibitor>

[0416] The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer.

[0417] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, and a triazine ring), compounds having a thiourea and a mercaptoalkyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

[0418] Furthermore, an ion capture agent that captures anions such as halogen ions may also be used.

[0419] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. WO2015 / 199219, etc. can be used.

[0420] Specific examples of the migration inhibitor include the following compounds.

[0421] [Chemical formula 37]

[0422]

[0423] When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass based on the total solid content of the photosensitive resin composition.

[0424] The migration inhibitor may be one kind or two or more kinds. When there are two or more kinds of migration inhibitors, the total amount thereof is preferably within the above range.

[0425] <Polymerization inhibitor>

[0426] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

[0427] As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, Ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO2015 / 125469 can also be used.

[0428] Furthermore, the following compounds (Me is methyl group) can also be used.

[0429] [Chemical formula 38]

[0430]

[0431] When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass based on the total solid content of the photosensitive resin composition of the present invention.

[0432] The polymerization inhibitor may be one kind or two or more kinds. When the polymerization inhibitor is two or more kinds, the total amount thereof is preferably within the above range.

[0433] <Metal Adhesion Improver>

[0434] The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode or wiring, etc. Examples of the metal adhesion improver include a silane coupling agent and the like.

[0435] Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. WO2015 / 199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. WO2011 / 080992A1, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. WO2014 / 097594. It is also preferred to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. Furthermore, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[0436] [Chemical formula 39]

[0437]

[0438] Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfur-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can be used.

[0439] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer precursor, more preferably in the range of 0.5 to 15 parts by mass, and further preferably in the range of 0.5 to 5 parts by mass. By setting it to above the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The metal adhesion improver can be only one or more than two. When using two or more, it is preferred that the total is the above range.

[0440] <Other additives>

[0441] The photosensitive resin composition of the present invention can be blended with various additives as needed, such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, etc., within a range that does not impair the effects of the present invention. When these additives are blended, the total amount thereof is preferably set to 3% by mass or less of the solid content of the composition.

[0442] <<Sensitizing pigment>>

[0443] The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state contacts a thermal curing accelerator, a thermal free radical polymerization initiator, a photo-free radical polymerization initiator, etc., and produces effects such as electron transfer, energy transfer, and heat generation. As a result, the thermal curing accelerator, the thermal free radical polymerization initiator, and the photo-free radical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. For details about the sensitizing dye, reference can be made to the records of paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, and the contents are incorporated into this specification.

[0444] When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The sensitizing dye may be used alone or in combination of two or more.

[0445] <<Chain transfer agent>>

[0446] The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These generate free radicals by supplying hydrogen to low-activity free radicals, or by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

[0447] Furthermore, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. WO2015 / 199219 can also be used.

[0448] When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be only one or more than two. When there are two or more chain transfer agents, the total range is preferably the above range.

[0449] <<Surfactant>>

[0450] From the viewpoint of further improving the coating property, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants, etc. can be used. In addition, the following surfactants are also preferred.

[0451] [Chemical formula 40]

[0452]

[0453] Furthermore, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. WO2015 / 199219 can also be used.

[0454] When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The surfactant may be only one or two or more. When there are two or more surfactants, the total range is preferably the above range.

[0455] <<Higher fatty acid derivatives>>

[0456] In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention so that a part of the derivative exists on the surface of the composition during the drying process after coating.

[0457] Furthermore, as the higher fatty acid derivatives, compounds described in paragraph 0155 of International Publication No. WO2015 / 199219 can also be used.

[0458] When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total range is preferably the above range.

[0459] <Regulation on other substances contained>

[0460] From the viewpoint of the coating surface state, the water content of the photosensitive resin composition of the present invention is preferably less than 5 mass %, more preferably less than 1 mass %, and further preferably less than 0.6 mass %.

[0461] From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When multiple metals are included, the total amount of these metals is preferably within the above range.

[0462] In addition, as a method for reducing metal impurities accidentally contained in the photosensitive resin composition of the present invention, there can be cited methods such as selecting a raw material with a low metal content as a raw material constituting the photosensitive resin composition of the present invention, filtering the raw material constituting the photosensitive resin composition of the present invention through a filter, lining the inside of an apparatus with polytetrafluoroethylene, and performing distillation under conditions that suppress contamination as much as possible.

[0463] Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, the content in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably in the above range.

[0464] As the storage container of the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the composition, it is also preferable to use a multilayer bottle having an inner wall of the container composed of six types of six layers of resins, or a bottle having a seven-layer structure of six types of resins. Examples of such containers include the containers described in Japanese Patent Application Publication No. 2015-123351.

[0465] <Preparation of Composition>

[0466] The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and the mixing can be performed by a conventionally known method.

[0467] Furthermore, for the purpose of removing foreign matter such as garbage or particles in the composition, it is preferred to perform filtration using a filter. The filter pore size is preferably less than 1 μm, more preferably less than 0.5 μm, and further preferably less than 0.1 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can use a filter pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a cycle filtration. Furthermore, filtering can be performed after pressurization. When filtering after pressurization, the pressure of pressurization is preferably greater than 0.05 MPa and less than 0.3 MPa.

[0468] In addition to filtering using a filter, an impurity removal process using an adsorbent may be performed. Filter filtering and impurity removal process using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[0469] <Cured film, laminate, semiconductor element, and method for producing the same>

[0470] Next, a cured film, a laminated body, a semiconductor element, and methods for producing these will be described.

[0471] The cured film of the present invention is formed by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Also, as an upper limit, it can be 100 μm or less, and can also be 30 μm or less.

[0472] The cured film of the present invention may be laminated in two or more layers, and further in 3 to 7 layers to form a laminate. The laminate having two or more cured films of the present invention preferably has a metal layer between the cured films. These metal layers can be preferably used as metal wiring such as a redistribution layer.

[0473] As the fields to which the cured film of the present invention can be applied, there can be cited insulating films of semiconductor elements, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, there can be cited sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), or the case where the insulating films for actual installation purposes such as the above are patterned by etching, etc. For these uses, for example, reference can be made to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaaki / Supervision, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011 Issue, Japan Polyimide and Aromatic Polymer Research Society / Editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

[0474] Furthermore, the cured film of the present invention can also be used in the production of offset printing plates, screen printing plates and the like, in etching of molded parts, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0475] The method for producing a cured film of the present invention includes the case of using the photosensitive resin composition of the present invention. Specifically, it is preferred to include the following steps (a) to (d).

[0476] (a) Film forming step of applying the photosensitive resin composition to a substrate to form a film

[0477] (b) After the film forming step, an exposure step of exposing the film

[0478] (c) A development step of developing the exposed photosensitive resin composition layer

[0479] (d) a heating step of heating the developed photosensitive resin composition at 80 to 450° C.

[0480] As in this embodiment, the exposed resin layer can be further cured by heating after development. In this heating step, the thermal base generator of the present invention acts to obtain sufficient curability.

[0481] The method for manufacturing a laminated body according to a preferred embodiment of the present invention includes a method for manufacturing a cured film according to the present invention. The method for manufacturing a laminated body according to the present embodiment is to form a cured film according to the method for manufacturing a cured film, and then, the process (a) or the processes (a) to (c) or the processes (a) to (d) are performed again. In particular, it is preferred to perform the above-mentioned processes multiple times, for example 2 to 5 times (i.e., 3 to 6 times in total) in sequence. By stacking the cured films in this way, a laminated body can be formed. In the present invention, it is particularly preferred to provide a metal layer on the upper side of the portion where the cured film is provided or between the cured films or in both. In addition, in the manufacture of the laminated body, it is not necessary to repeat all the processes (a) to (d). As described above, a laminated body of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times.

[0482] <<Film forming step (layer forming step)>>

[0483] The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying the photosensitive resin composition to a substrate to form a film (layer).

[0484] The type of substrate can be appropriately set according to the application, but is not particularly limited, and includes semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates of plasma display panels (PDPs). In the present invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates are more preferred.

[0485] Furthermore, when the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.

[0486] As a method of applying the photosensitive resin composition to a substrate, coating is preferred.

[0487] Specifically, as an applicable method, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, spin coating, slit coating, spray coating, and inkjet are more preferred. According to the method, the appropriate solid content concentration or coating conditions are adjusted, thereby obtaining a resin layer of the desired thickness. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating or spray coating, inkjet, etc. are preferably used, and as long as it is a rectangular substrate, slit coating or spray coating, inkjet, etc. are preferably used. When it is a spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

[0488] <<Drying process>>

[0489] The manufacturing method of the present invention may further include a drying step for removing the solvent after forming the photosensitive resin composition layer and after the film forming step (layer forming step). The preferred drying temperature is 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

[0490] <<Exposure process>>

[0491] The manufacturing method of the present invention may include an exposure step of exposing the photosensitive resin composition layer. The exposure amount is not particularly limited within a range that allows the photosensitive resin composition to be cured. For example, the exposure energy at a wavelength of 365 nm is preferably 100 to 10,000 mJ / cm 2 , more preferably irradiation 200 to 8000 mJ / cm 2 .

[0492] The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, and is preferably 240 to 550 nm.

[0493] Regarding the exposure wavelength, if described in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, etc. Regarding the photosensitive resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and among them, exposure by i-rays is preferred. In this way, particularly high exposure sensitivity can be obtained.

[0494] <<Development Process>>

[0495] The manufacturing method of the present invention may include a development process, in which the exposed photosensitive resin composition layer is developed. By developing, the unexposed portion (non-exposed portion) is removed. There is no particular limitation on the development method as long as the desired pattern can be formed. For example, a development method such as spin immersion, spraying, dipping, or ultrasonic wave can be used.

[0496] Development is performed using a developer. As for the developer, any developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion). The developer preferably contains an organic solvent, and the developer more preferably contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula into ChemBioDraw.

[0497] As for the organic solvent, examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl 2-ethoxy-2-methylpropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be suitably mentioned; as the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be suitably mentioned; and as the sulfoxides, dimethyl sulfoxide can be suitably mentioned.

[0498] In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

[0499] The developer preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of an organic solvent. Furthermore, 100% by mass of the developer may be an organic solvent.

[0500] The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but development can be performed usually at 20 to 40°C.

[0501] After the treatment with the developer, rinsing may be further performed. The rinsing is preferably performed with a solvent different from the developer. For example, the solvent contained in the photosensitive resin composition may be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

[0502] <<Heating process>>

[0503] The manufacturing method of the present invention preferably includes a heating step after the film forming step (layer forming step), the drying step or the developing step. In the heating step, a cyclization reaction of the polymer precursor is carried out. In addition, the composition of the present invention may contain a free radical polymerizable compound other than the polymer precursor, and can perform curing of the free radical polymerizable compound other than the unreacted polymer precursor in this step. As the heating temperature (maximum heating temperature) of the layer in the heating step, it is preferably 50°C or more, more preferably 80°C or more, further preferably 140°C or more, further preferably 150°C or more, further preferably 160°C or more, and further preferably 170°C or more. As the upper limit, it is preferably 500°C or less, more preferably 450°C or less, further preferably 350°C or less, further preferably 250°C or less, and further preferably 220°C or less.

[0504] Regarding heating, it is preferred to perform the heating at a heating rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the heating rate to 1°C / min or more, it is possible to ensure productivity while preventing excessive volatilization of amines, and by setting the heating rate to 12°C / min or less, it is possible to relax the residual stress of the cured film.

[0505] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The temperature at the start of heating means the temperature at the start of the process of heating to the maximum heating temperature. For example, after applying the photosensitive resin composition to a substrate and drying it, it is the temperature of the dried film (layer), for example, preferably gradually increasing the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition.

[0506] The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

[0507] In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, it is preferably heated at a heating temperature of 180° C. to 320° C., and more preferably at 180° C. to 260° C. The reason for this is not clear, but it is believed that the following is the reason, that is, at this temperature, the acetylene groups of the polymer precursors between the layers undergo a cross-linking reaction.

[0508] Heating can be carried out in stages. As an example, the pretreatment process can be performed by heating from 25°C to 180°C at 3°C / min and keeping at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C / min, and keeping at 200°C for 120 minutes. The heating temperature of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In the pretreatment process, it is also preferred to treat while irradiating ultraviolet rays as described in the gazette of U.S. Patent No. 9159547. The properties of the film can be improved by these pretreatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a process of more than two stages, for example, pretreatment process 1 can be carried out in the range of 100-150°C, and then pretreatment process 2 can be carried out in the range of 150-200°C.

[0509] Furthermore, the heating may be followed by cooling. In this case, the cooling rate is preferably 1 to 5° C. / min.

[0510] The heating step is preferably performed in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[0511] <<Metal layer forming process>>

[0512] The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.

[0513] The metal layer is not particularly limited, and any conventional metal can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further preferred.

[0514] The formation method of the metal layer is not particularly limited, and existing methods can be used. For example, the method described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and the method of combining these etc. can be considered. More specifically, the patterning method formed by combining sputtering, photolithography and etching, and the patterning method formed by combining photolithography and electrolytic plating can be cited.

[0515] The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm in the thickest portion.

[0516] <<Lamination process>>

[0517] The production method of the present invention preferably further includes a lamination step.

[0518] The lamination process is a series of processes including, on the surface of the cured film (resin layer) or the metal layer, performing (a) a film forming process (layer forming process), (b) an exposure process, (c) a developing process, and (d) a heating process in sequence again. Among them, it can be a method in which only the film forming process (a) is repeated. In addition, it can also be a method in which the heating process (d) is performed at the end or in the middle of the lamination. That is, it can also be set as follows: the processes (a) to (c) are repeated a predetermined number of times, and then the heating (d) is performed, thereby the laminated photosensitive resin composition layer is cured collectively. In addition, the metal layer forming process (e) can be included after the (c) developing process, and in this case, the heating (d) can be performed each time, or the heating (d) can be performed collectively after the predetermined number of laminations. It is beyond doubt that the lamination process can also appropriately include the above-mentioned drying process and heating process.

[0519] When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the heating step and after the exposure step or after the metal layer forming step. As the surface activation treatment, plasma treatment is exemplified.

[0520] The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

[0521] For example, a structure of 3 or more and 7 or less resin layers such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferred, and 3 or more and 5 or less layers is more preferred.

[0522] In the present invention, in particular, after the metal layer is provided, it is further preferred to form a cured film (resin layer) of the photosensitive resin composition in a manner that covers the metal layer. Specifically, there can be mentioned a method of sequentially repeating (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step, or a method of sequentially repeating (a) a film forming step, (b) an exposure step, (c) a developing step, and (e) a metal layer forming step, and collectively providing (d) a heating step at the end or in the middle. By alternately performing a lamination step of laminating a photosensitive resin composition layer (resin) and a metal layer forming step, it is possible to alternately laminate a photosensitive resin composition layer (resin layer) and a metal layer.

[0523] The present invention also discloses a semiconductor element having the cured film or laminate of the present invention. As a specific example of a semiconductor element using the photosensitive resin composition of the present invention in the formation of an interlayer insulating film for a redistribution layer, reference can be made to the description in paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in FIG. 1 , which are incorporated into this specification.

[0524] Example

[0525] Below, give embodiment and the present invention is further described in detail.About the material shown in the following embodiment, usage, ratio, processing content, processing step etc., as long as do not depart from the purpose of the present invention, then can be appropriately changed.Thereby, the scope of the present invention is not limited to the specific example shown below.Unless otherwise stated, then "part", "%" is a mass reference.

[0526] <Synthesis Example 1: Synthesis of Thermal Alkali Generator BE-1>

[0527] In a flask equipped with a condenser, 6.00 g of 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 35.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.), and the mixture was cooled to 0° C. Then, 5.96 g of phenyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 10.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.), and the mixture was added dropwise over 1 hour. After the addition, the mixture was stirred at room temperature for 2 hours, poured into 300 mL of 0.5 N hydrochloric acid water, and the precipitate was filtered, washed with 100 mL of water and a mixed solution of acetone / methanol, and dried at 40° C. for 8 hours to obtain 7.2 g of a thermal base generator BE-1 having the following structure.

[0528] [Chemical formula 41]

[0529]

[0530] <Synthesis Example 2: Synthesis of Thermal Alkali Generator BE-2>

[0531] In a flask equipped with a condenser, 7.20 g of 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 41.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.) and cooled to 0°C. Next, 6.67 g of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the addition, the mixture was stirred at room temperature for 2 hours, and the precipitate was filtered, rinsed with 50 mL of N-methylpyrrolidone, reslurried and washed with 400 mL of acetone for 1 hour, and filtered. After drying at 40°C for 8 hours, 6.8 g of a thermal base generator BE-2 having the following structure was obtained.

[0532] [Chemical formula 42]

[0533]

[0534] <Synthesis Example 3: Synthesis of Thermal Alkali Generator BE-3>

[0535] In a flask with a condenser, 6.48 g of 3,3'-dihydroxybenzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 40.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.) and cooled to 0°C. Next, 7.65 g of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the addition, the mixture was stirred at room temperature for 2 hours, the precipitate was filtered, rinsed with 50 mL of N-methylpyrrolidone, re-pulped and washed with 400 mL of acetone for 1 hour, and filtered. After drying at 40°C for 8 hours, 9.8 g of a thermal base generator BE-3 having the following structure was obtained.

[0536] [Chemical formula 43]

[0537]

[0538] <Synthesis Example 4: Synthesis of Thermal Alkali Generator BE-4>

[0539] In a flask with a condenser, 3.15 g of 3,3'-dihydroxybenzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 g of cyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 35.0 g of N,N-dimethylacetamide (manufactured by KANTO CHEMICAL CO., INC.). Next, 2.91 g of 1,3-bis(isocyanatomethyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the addition, the mixture was stirred at room temperature for 1 hour, and 15 mL of methanol was added and dissolved. The mixture was poured into a mixed solution of 400 mL of methanol and 400 mL of water, the precipitate was filtered, and the mixture was rinsed with 100 mL of water and 100 mL of methanol in sequence, and filtered. 5.2 g of a thermal base generator (resin) BE-4 having the following structure was obtained by drying at 40°C for 8 hours. The weight average molecular weight of the above resin is 20,300.

[0540] [Chemical formula 44]

[0541]

[0542] <Synthesis Example 5: Synthesis of Polyimide Precursor Resin A-1 from Oxydiphthalic Anhydride, 4,4'-diphthalic Anhydride, 2-Hydroxyethyl Methacrylate, and 4,4'-Diaminodiphenyl Ether>

[0543] In a dry reactor equipped with a stirrer, a condenser and a flat-bottomed joint with an internal thermometer, 10.0 g (32.25 mmol) of oxydiphthalic anhydride was suspended in 140 mL of diethylene glycol dimethyl ether while removing water. Then, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, the mixture was heated to room temperature, stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, a solution of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. The polyimide precursor resin (A-1) has Mw=24800 and Mn=10500.

[0544] <Synthesis Example 6: Synthesis of Polyimide Precursor Resin A-2 from Oxydiphthalic Anhydride, 2-Hydroxyethyl Methacrylate, and 4,4'-Diaminodiphenyl Ether>

[0545] In a dry reactor equipped with a stirrer, a condenser and a flat-bottomed joint with an internal thermometer, 20.0 g (64.5 mmol) of oxydiphthalic anhydride was suspended in 140 mL of diethylene glycol dimethyl ether while removing water. Then, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, the mixture was heated to room temperature, stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, a solution of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. The polyimide precursor resin (A-2) had Mw = 23500 and Mn = 8800.

[0546] <Examples and Comparative Examples>

[0547] The components listed in the following table were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm. Furthermore, each photosensitive resin composition was evaluated for elongation at break and storage stability.

[0548]

[0549] <Components of the photosensitive resin composition>

[0550] The details of the components constituting each photosensitive resin composition are as follows.

[0551] (A) Polymer precursor: A-1 and A-2 synthesized above

[0552] (B) Specific thermal base generator: BE-1 to BE-4 synthesized above

[0553] Alkali generating agent used in comparative example: the following compound

[0554] [Chemical formula 45]

[0555]

[0556] (C) Solvent

[0557] DMSO: dimethyl sulfoxide

[0558] GBL: gamma-butyrolactone

[0559] The mixing ratio of DMSO to GBL was 20:80 by mass.

[0560] (D) Photopolymerization initiator (all trade names)

[0561] OXE-01: IRGACURE OXE 01 (manufactured by BASF)

[0562] OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[0563] (E) Polymerizable compounds (all trade names)

[0564] SR-209: SR-209 (manufactured by Sartomer Company, Inc.)

[0565] SR-231: SR-231 (manufactured by Sartomer Company, Inc.)

[0566] SR-239: SR-239 (manufactured by Sartomer Company, Inc.)

[0567] (F) Inhibitor

[0568] F-1: 1,4-Benzoquinone

[0569] F-2: 4-Methoxyphenol

[0570] F-3: 1,4-dihydroxybenzene

[0571] (G) Metal Adhesion Improver

[0572] G-1: The following compound

[0573] G-2: The following compounds

[0574] G-3: The following compounds

[0575] Et represents ethyl.

[0576] [Chemical formula 46]

[0577]

[0578] (H) Migration inhibitor

[0579] H-1: 1H-tetrazole

[0580] H-2: 1,2,4-triazole

[0581] H-3: 5-phenyltetrazolyl

[0582] (I) Other thermal alkali generating agents

[0583] I-1:

[0584] [Chemical formula 47]

[0585]

[0586] <Evaluation of elongation at break (film strength measurement)>

[0587] Each photosensitive resin composition described in the above table was applied to a silicon wafer by spin coating to form a photosensitive resin composition layer. The silicon wafer formed with the obtained photosensitive resin composition layer was dried on a hot plate at 100°C for 5 minutes, thereby obtaining a photosensitive resin composition layer with a uniform thickness of about 15μm on the silicon wafer. The obtained thermal photosensitive resin composition layer (resin layer) was heated at a heating rate of 10°C / min under a nitrogen atmosphere, and after reaching 250°C, it was heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9% hydrofluoric acid solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was used to make a test piece with a width of 3mm and a sample length of 30mm using a punching machine. Using a tensile testing machine (TENSILON), at a crosshead speed of 300mm / min, at 25°C and 65%RH (relative humidity), the obtained test piece was measured in the long side direction of the film in accordance with JIS-K6251. The evaluation was performed 5 times each, and the average value of the elongation when the film was broken (elongation at break) was used.

[0588] A 60% or more

[0589] B 55% or more and less than 60%

[0590] C 50% or more and less than 55%

[0591] D less than 50%

[0592] <Evaluation of storage stability (measurement of film thickness change rate)>

[0593] <<Film thickness before time>>

[0594] Each photosensitive resin composition described in the above table was applied to a silicon wafer by spin coating to form a photosensitive resin composition layer. The silicon wafer formed with the obtained photosensitive resin composition layer was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a photosensitive resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. This value was taken as the film thickness before aging.

[0595] <<Film thickness after time>>

[0596] Each photosensitive resin composition described in the above table was placed in a glass container and sealed, and after standing for 14 days in an environment of 25°C, it was applied to a silicon wafer by spin coating at the same rotation speed as when the film thickness before time was obtained to form a photosensitive resin composition layer. The silicon wafer on which the obtained photosensitive resin composition layer was formed was dried on a hot plate at 100°C for 5 minutes, thereby obtaining a uniform photosensitive resin composition layer on the silicon wafer. The film thickness of the obtained photosensitive resin composition layer was measured in the same manner as above, and the value was taken as the film thickness after time.

[0597] <<Film thickness change rate>>

[0598] The film thickness change rate was calculated by the following formula.

[0599] Film thickness change rate [%] = |film thickness before time - film thickness after time| / film thickness before time × 100

[0600] Evaluation level and film thickness change rate

[0601] A: Less than 10%

[0602] B: 10% or more and less than 15%

[0603] C: 15% or more and less than 20%

[0604] D: 20% or more

[0605] The above results show that the photosensitive resin composition containing a specific thermal base generator and a heterocyclic polymer-containing precursor is excellent in curability and storage stability.

[0606] <Example 100>

[0607] The photosensitive resin composition of Example 1 was filtered under pressure through a filter having a pore width of 1.0 μm, and then applied to the surface of a resin substrate having a thin copper layer formed thereon by rotation (3500 rpm, 30 seconds). The photosensitive resin composition applied to the resin substrate was dried at 100°C for 2 minutes, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). The photosensitive resin composition was exposed to light at a wavelength of 365 nm at 200 mJ / cm 2After exposure, the film was baked, developed with cyclopentanone for 30 seconds, and rinsed with PGMEA for 20 seconds to obtain a pattern.

[0608] Then, the film was heated at 230° C. for 3 hours to form an interlayer insulating film for a redistribution layer. The interlayer insulating film for a redistribution layer had excellent insulating properties.

Claims

1. A photosensitive resin composition comprising: A thermal base generating agent represented by the following formula (N1), and At least one precursor compound of a polyimide precursor and a polybenzoxazole precursor; In formula (N1), X N represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, Z N represents an oxygen atom or a sulfur atom, R N1 and R N2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N From the adjacent nitrogen atom to X N and a trivalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain. * Each independently represents a hydrogen atom or a monovalent organic group, L N Optionally have in addition to X N Substituents other than The content of the thermal base generator is 0.5 to 30% by mass based on the total solid content of the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein In the formula (N1), L N At least a part of the connecting chain in is a part of the arylene group.

3. The photosensitive resin composition according to claim 1, wherein The thermal base generator is a compound represented by formula (N2), In formula (N2), X N1 and X N2 each independently represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, Z N1 represents an oxygen atom or a sulfur atom, R N3 and R N4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N1 and L N2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, n1 represents 0 or 1, n2 represents an integer from 0 to 10, The sum of n1 and n2 is greater than 1, n3 represents an integer greater than 1, When n1=1, L N1 From the adjacent nitrogen atom to X N1 is a divalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain, When n2≥1, L N2 From the adjacent nitrogen atom to X N2 The 1+n2-valent hydrocarbon group is a hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

4. The photosensitive resin composition according to claim 3, wherein In the formula (N2), X N1 and X N2 The total number and Z N1 The total number is equal.

5. The photosensitive resin composition according to claim 3 or 4, wherein In the formula (N2), L N1 and L N2 At least a part of the connecting chain in is a part of the arylene group.

6. The photosensitive resin composition according to claim 1, wherein The thermal base generator is a polymer compound comprising a repeating unit represented by formula (N3), In formula (N3), X N3 represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, Z N2 represents an oxygen atom or a sulfur atom, R N5 and R N6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N3 From the adjacent nitrogen atom to X N3 and a trivalent hydrocarbon group having 2 to 6 atoms constituting the connecting chain. L N3 Optionally have in addition to X N3 Other substituents.

7. The photosensitive resin composition according to claim 6, wherein The thermal base generator is a polymer compound comprising a repeating unit represented by formula (N4), In formula (N4), X N4 each independently represents any one of a hydroxyl group, a carboxyl group and a sulfonic acid group, With Z N2 Independently, Z N3 represents an oxygen atom or a sulfur atom, With R N5 and R N6 Independently, R N7 and R N8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, L N4 From the adjacent nitrogen atom to X N4 and 2 to 6 hydrocarbon groups constituting the connecting chain, L N5 It represents a divalent organic group.

8. The photosensitive resin composition according to claim 7, wherein The L N4 At least a part of the connecting chain in is a part of the arylene group.

9. The photosensitive resin composition according to claim 1 or 2, wherein X in the formula (N1) N It is a hydroxyl group or a carboxyl group.

10. The photosensitive resin composition according to claim 3 or 4, wherein X in the formula (N2) N1 or X N2 It is a hydroxyl group or a carboxyl group.

11. The photosensitive resin composition according to any one of claims 6 to 8, wherein X in the formula (N3) N3 It is a hydroxyl group or a carboxyl group.

12. The photosensitive resin composition according to claim 7 or 8, wherein X in the formula (N4) N4 It is a hydroxyl group or a carboxyl group. 13 . The photosensitive resin composition according to claim 1 , further comprising a photoradical polymerization initiator and a radical polymerizable compound.

14. The photosensitive resin composition according to any one of claims 1 to 4, wherein The precursor compound includes a polyimide precursor.

15. The photosensitive resin composition according to claim 14, wherein The polyimide precursor has a structural unit represented by the following formula (1): In formula (1), A 1 and A 2 Each independently represents an oxygen atom or NH, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group.

16. The photosensitive resin composition according to claim 15, wherein R of the formula (1) 113 and R 114 At least one of the compounds comprises a free radical polymerizable group. 17 . The photosensitive resin composition according to claim 1 , which is used for forming an interlayer insulating film for a redistribution layer. 18 . A cured film obtained by curing the photosensitive resin composition according to claim 1 . 19 . A laminate comprising two or more layers of the cured film according to claim 18 , and comprising a metal layer between the cured films. 20 . A method for producing a cured film, comprising a film forming step of applying the photosensitive resin composition according to claim 1 to a substrate to form a film. 21 . The method for producing a cured film according to claim 20 , comprising the step of heating the film at 50° C. to 450° C. 22 . A semiconductor element comprising the cured film according to claim 18 or the laminated body according to claim 19 .

Images