Photosensitive resin composition, cured film, laminate and method for producing the same, semiconductor device and thermal base generator used therein

Abstract

The present invention provides a photosensitive resin composition, a cured film, a laminate, and methods for producing the same, a semiconductor device, and a thermal base generator used therein. The photosensitive resin composition contains a specific thermal base generator, at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a photosensitizer, and the total content of acid groups and acid generating groups contained in the polymer precursor and the photosensitizer is 0.5 mmol / g or less.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing the same, a semiconductor device, and a thermal base generator used therein. Background Art

[0002] Polyimide resin and polybenzoxazole resin are excellent in heat resistance and insulation, and therefore are suitable for various applications (for example, refer to non-patent literature 1 and 2). The application is not particularly limited. If a semiconductor device for mounting is used as an example, the use as a material for an insulating film and a sealing material or a protective film thereof can be cited. In addition, it is also used as a base film and a coating film of a flexible substrate.

[0003] The above-mentioned polyimide resin etc. are usually dissolved in low solubility of solvent. Therefore, the precursor before the cyclization reaction is mostly used as a method for dissolving in a solvent under the state of a polymer precursor such as a polyimide precursor and a polybenzoxazole precursor. Thus, it is possible to achieve excellent handling properties, so that it is possible to apply to the various forms such as substrates to process when manufacturing the above-mentioned products. Afterwards, the polymer precursor is heated and cyclized, so that a solidified product can be formed. In addition to the high performance such as heat resistance and insulation properties possessed by polyimide resin etc., from the viewpoint of excellent adaptability in this manufacturing, it is expected that the application in this industry will be gradually carried out.

[0004] There is a resin proposed as a material for coating by utilizing the above characteristics (Patent Document 1). The photosensitive resin composition contains (A) a polyimide precursor, (B) a specific plasticizer, and (C) a photosensitizer. It is described that a product having flexibility, no warping, and exhibiting flame retardancy can be provided.

[0005] In order to be used as an insulating resin for a rewiring layer, a thermosetting resin composition containing a specific tertiary amine compound and a thermosetting resin cured by alkali cyclization is proposed (Patent Document 2). It is recorded that the cyclization reaction can be carried out at low temperatures, so the stability is excellent. In addition, a photosensitive resin composition is proposed, which contains a compound having an anion part, a heterocyclic polymer precursor and a free radical polymerizable compound in consideration of being used as an insulating film for a rewiring layer, and the compound containing the anion part has a specific quaternary ammonium (cation part) and free radical initiation energy (Patent Document 3). It is recorded that the cyclization reaction can be carried out at low temperatures, and the resolution in exposure and development is excellent.

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2009-109590

[0009] Patent Document 2: International Publication No. 2015 / 199220

[0010] Patent Document 3: Japanese Patent Application Publication No. 2016-027357

[0011] Non-patent literature

[0012] Non-patent document 1: Science & Technology Co., Ltd. "High-functionalization of polyimide and its application technology" April 2008

[0013] Non-patent literature 2: Masaaki Kakimoto / Editor, CMC Technical library "Basics and Development of Polyimide Materials" published in November 2011 Summary of the invention

[0014] Technical issues to be solved by the invention

[0015] By the above-mentioned technology, a photosensitive resin composition suitable for interlayer insulating films and rewiring layers, etc., which is cyclized at low temperatures and has excellent stability and resolution can be provided. On the other hand, as the development speed of semiconductor devices is further accelerated, from the perspective of strengthening the improvement of a part of the performance, it is strongly required to improve the overall performance. Therefore, in view of the use in interlayer insulating films and rewiring layers, etc., the present invention aims to provide a photosensitive resin composition and a cured film, a laminate, a method for manufacturing a cured film, a method for manufacturing a laminate, a semiconductor device, and a thermal alkali generator, wherein the photosensitive resin composition satisfies the performance required for the photosensitive resin composition at a high standard, namely, storage stability, mechanical properties, developer solubility of the unexposed part, and photolithography, and is generally excellent.

[0016] Means for solving technical problems

[0017] Based on the above problems, the present inventors have repeatedly studied and experimented on the formulations and formulas, preparation conditions, etc. for improving the overall performance of the composition containing the polymer precursor from various viewpoints. As a result, it was found that the above problems can be solved by limiting the thermal base generator used in combination with the polymer precursor to specific substances, thereby completing the present invention. Specifically, the above problems are solved by the following methods <1> and <2> to <23>.

[0018] <1> A photosensitive resin composition comprising:

[0019] At least one thermal base generating agent selected from the group consisting of a thermal base generating agent represented by the following formula (B1) and a thermal base generating agent represented by the following formula (B2);

[0020] At least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and

[0021] Photosensitive agent,

[0022] The total content of the acid group and the acid generating group contained in the polymer precursor and the photosensitizer is 0.5 mmol / g or less.

[0023] [Chemical formula 1]

[0024]

[0025] In formula (B1) and (B2), R 1 , R 2 and R 3 are independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom, wherein R 1 and R 2 are not hydrogen atoms at the same time, and R 1 , R 2 and R 3 It does not have a carboxyl group.

[0026] <2> The photosensitive resin composition according to <1>, wherein the base generation temperature of the thermal base generator is 120° C. or higher and 200° C. or lower.

[0027] <3> The photosensitive resin composition according to <1> or <2>, wherein the thermal base generator has a pKa of greater than 7.

[0028] <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymer precursor includes a polyimide precursor.

[0029] <5> The photosensitive resin composition according to <4>, wherein the polyimide precursor is represented by the following formula (1);

[0030] [Chemical formula 2]

[0031]

[0032] 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.

[0033] <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the molar absorption coefficient of the thermal base generator at a wavelength of 365 nm is 100 l / (mol·cm) or less.

[0034] <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the thermal base generator includes a thermal base generator that generates a base having a conjugate acid pKa of 10 or more by heating.

[0035] <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the photosensitizer contains a photopolymerization initiator.

[0036] <9> The photosensitive resin composition according to any one of <1> to <8>, which is used for development using a developer containing 90% by mass or more of an organic solvent.

[0037] <10> The photosensitive resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a redistribution layer.

[0038] <11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10>.

[0039] <12> The cured film according to <11>, wherein the film thickness is 1 to 30 μm.

[0040] <13> A laminate having two or more layers of the cured film according to <11> or <12>.

[0041] <14> A laminate having 3 to 7 or more cured films according to <11> or <12>.

[0042] <15> The laminate according to <13> or <14>, comprising a metal layer between the cured films.

[0043] <16> A method for producing a cured film, the method comprising a film forming step of applying the photosensitive resin composition according to any one of <1> to <10> to a substrate to form a film.

[0044] <17> The method for producing a cured film according to <16>, further comprising an exposure step of exposing the film to light and a development step of developing the film.

[0045] <18> The method for producing a cured film according to <17>, wherein the developer used in the development contains 90% by mass or more of an organic solvent.

[0046] <19> The method for producing a cured film according to any one of <16> to <18>, comprising the step of heating the film at 80 to 450°C.

[0047] <20> A method for producing a laminate, comprising performing the method for producing a cured film according to any one of <16> to <19> a plurality of times.

[0048] <21> A semiconductor device comprising the cured film according to <11> or <12> or the laminate according to any one of <13> to <15>.

[0049] <22> A thermal base generating agent represented by the following formula (B1) or formula (B2);

[0050] [Chemical formula 3]

[0051]

[0052] In formula (B1) and (B2), R 1 , R 2 and R 3 are independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom, wherein R 1 and R 2 are not hydrogen atoms at the same time, and R 1 , R 2 and R 3 It does not have a carboxyl group.

[0053] <23> The thermal base generator according to <22>, which is used for a photosensitive resin composition developed using a developer containing 90% by mass or more of an organic solvent.

[0054] Effects of the Invention

[0055] The photosensitive resin composition of the present invention is required to be used in an interlayer insulating film or a rewiring layer, and is generally excellent in storage stability, mechanical properties, solubility in a developer of an unexposed portion, and photolithography properties. In addition, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, a semiconductor device, and a thermal base generator using the photosensitive resin composition can be provided. DETAILED DESCRIPTION

[0056] Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0057] Although the description of the constituent elements in the present invention described below may be based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0058] Regarding the marking of groups (atomic groups) in this specification, the marking that does not record substitution and unsubstituted includes both groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0059] In this specification, "exposure" is included in exposure, unless otherwise specified, including exposure using light, and drawing using particle beams such as electron beams and ion beams. In addition, as light used for exposure, active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams can be generally cited.

[0060] In the present specification, “(meth)acrylate” means both “acrylate” and “methacrylate” or either one of them, “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid” or either one of them, and “(meth)acryloyl” means both “acryloyl” and “methacryloyl” or either one of them.

[0061] In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the intended effect of the process can be achieved.

[0062] In this specification, solid content refers to the mass percentage of other components excluding the solvent relative to the total mass of the composition. In addition, the temperature in this specification is 23° C. unless otherwise specified.

[0063] In this specification, as long as there is no special record, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement) and are defined as styrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (TOSOH CORPORATION system), and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel SuperHZ2000 (TOSOH CORPORATION system) as columns. As long as there is no special record, the eluent is set to the eluent measured by THF (tetrahydrofuran). And, as long as there is no special record, the detection is set to the detection of a wavelength 254nm detector using UV line (ultraviolet rays).

[0064] The photosensitive resin composition of the present invention (hereinafter, sometimes referred to as "the composition of the present invention" or "the resin composition of the present invention") is characterized by containing at least one thermal base generator selected from the group consisting of thermal base generators represented by formula (B1) and thermal base generators represented by formula (B2) (hereinafter, sometimes referred to as "specific thermal base generator"), at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and a photosensitive agent, and the total content of acid groups and acid generating groups contained in the above polymer precursor and the above photosensitive agent (hereinafter, this amount is sometimes referred to as "the amount of acid groups, etc.") is 0.5 mmol / g or less. By adopting this structure, a photosensitive resin composition having excellent storage stability, mechanical properties, developer solubility of unexposed parts, and photolithography properties can be obtained. The reasons for solving the above problems are considered to be as follows, including estimation.

[0065] In the photosensitive resin composition, the amount of acid groups contained in the polymer precursor is reduced, so that a material that can be developed more quickly in an organic solvent with low polarity can be prepared. The thermosetting film formed by the photosensitive resin composition that can be developed by an organic solvent is generally low in hygroscopicity and has excellent adhesion to the substrate and device reliability. On the other hand, the amount of acid groups in the polymer precursor is small, so if a basic compound is present in the composition, the cyclization reaction of the polymer precursor is easy to proceed. As a result, the storage stability is reduced. In the present invention, a specific thermal base generator having a structure that is roughly neutral before thermal decomposition and generates a base after thermal decomposition is used, thereby maintaining good curability based on the heating of the polymer precursor contained in the photosensitive resin composition and stably storing the photosensitive resin composition. In addition, the above-mentioned specific thermal base generator is preferably non-ionic, thereby enabling the organic solvent developability of the resin composition to be made even better.

[0066] <Specific thermal alkali generating agents>

[0067] The photosensitive resin composition of the present invention contains a thermal base generator (specific thermal base generator) represented by formula (B1) or formula (B2).

[0068] [Chemical formula 4]

[0069]

[0070] In formula (B1) and (B2), R 1 , R 2 and R 3 are independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and R 2 are not hydrogen atoms at the same time. 1 , R 2 and R 3It does not have a carboxyl group.

[0071] In addition, the tertiary amine structure in this specification refers to a structure in which the three bonds of the trivalent nitrogen atom are covalently bonded to the carbon atom of the hydrocarbon system. Therefore, when the bonded carbon atom is a carbon atom in the form of a carbonyl group, that is, when it forms an amide group together with the nitrogen atom, it is not limited to this. In the present invention, the organic group contained in the above-mentioned specific thermal base generator does not have a tertiary amine structure, and thus when the resist liquid is stored, the amidation reaction of the polymer in the solution is suppressed, so that the storage property of the resist liquid is excellent. In addition, each substituent does not have a carboxyl group, so that the solubility in organic solvents is excellent and the developability is excellent.

[0072] In formula (B1) and (B2), R is preferably 1 , R 2 and R 3 At least one of these contains a cyclic structure, and more preferably at least two contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring. By containing a cyclic structure, the solubility in an organic solvent becomes high, and the basicity and boiling point of the amine generated by thermal decomposition are high, so the amidation reaction of the polymer is more effectively promoted.

[0073] More specifically, R 1 and R 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). These groups may have a substituent T described below within the range in which the effect of the present invention is exerted. R 1 With R 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and R 2 In particular, preferably, it is a chain or cyclic, straight-chain or branched alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms) which may have a substituent T, more preferably, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms) which may have a substituent T, and further preferably, a cyclohexyl group which may have a substituent T.

[0074] As R 3, examples include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6), arylalkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), arylalkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and further preferably 8 to 16), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and arylalkoxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). Among them, preferred are cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups. 3 It may be further substituted with a substituent T within a range where the effects of the present invention are exhibited.

[0075] The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0076] [Chemical formula 5]

[0077]

[0078] In the formula, R 11 and R 12 and R 31 and R 32 Respectively with R in formula (B1) 1 and R 2 same.

[0079] R 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), and may have a substituent T within a range in which the effects of the present invention are exerted. 13 Preferred is an arylalkyl group.

[0080] R 33 and R 34Each of them is independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0081] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 12, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and is preferably an aryl group.

[0082] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[0083] [Chemical formula 6]

[0084]

[0085] R 11 and R 12 The definition of R in formula (B1-1) 11 and R 12 The definition is the same.

[0086] R 15 and R 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom or a methyl group.

[0087] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 12, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0088] The molecular weight of the specific thermal base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more. The molecular weight of the specific thermal base generator is within the above range, so that the solubility in an organic solvent is excellent and the developability is not deteriorated. In addition, the decomposition product after thermal decomposition is not likely to remain in the thermally cured film, and the reliability of the device is not impaired.

[0089] The base generation temperature of the specific thermal base generator is preferably 120° C. to 200° C., more preferably 130° C. to 180° C., and even more preferably 140° C. to 170° C. By controlling the temperature, curing by cyclization of the polymer precursor can be more reliably promoted. The base generation temperature can be measured as described in the examples described below.

[0090] Furthermore, the difference between the base generation temperature of the specific thermal base generator and the maximum temperature when heating for cyclizing the polymer precursor (maximum temperature - base generation temperature) is preferably 5° C. to 100° C., more preferably 10° C. to 80° C., and even more preferably 15° C. to 60° C. If it is within this range, the mechanical properties are further improved.

[0091] The base generated by the specific thermal base generator by heating preferably has a conjugate acid pKa of 10 or more, more preferably 11 or more, and further preferably 12 or more. The upper limit is practically 15 or less. The strong basicity makes the curability of the polymer precursor more effective.

[0092] The pKa of the specific thermal base generator is preferably greater than 7, more preferably 8 or more, and further preferably 9 or more. The upper limit is practically 12 or less. When the pKa is set within the above range, the basicity of the thermal base generator is weakened during storage, and the polymer precursor is not cured, thereby further improving its stability.

[0093] The specific thermal base generator preferably contains a neutral molecule. Neutral means electrically neutral, preferably a base that is not formed by anions or cations. Each atom in the molecule is linked by covalent bonding, and preferably a compound with a total charge of zero.

[0094] The pka can be measured by the method described in the Examples below.

[0095] The molar absorption coefficient of the specific thermal alkali generator contained in the photosensitive resin composition used in the present invention at a wavelength of 365 nm is preferably 500 l / (mol·cm) or less, more preferably 300 l / (mol·cm) or less, and further preferably 100 l / (mol·cm) or less. As the lower limit, it is actually 50 l / (mol·cm) or more. UV-2600 (manufactured by Shimadzu Corporation) was used as a measuring device for the molar absorption coefficient. Three samples were measured, and the value of the arithmetic average of the results was used. Other details were carried out in accordance with the contents described in JISK0115:2004 (Japanese Industrial Standards). In the present invention, it is preferred to use a thermal alkali generator whose absorption of light (i-ray) at a wavelength of 365 nm is suppressed to a low level as described above. As a result, the light transmittance and lithography properties during exposure will not be deteriorated, and more excellent mechanical properties can be achieved.

[0096] Examples of the substituent T include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and particularly preferably 2 to 6), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), a hydroxyalkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), a heteroaryl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 4; examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), a hydroxyl group, a primary or a secondary amino group (which may have 0 to 24 carbon atoms, 0 to 12 carbon atoms, or 0 to 6 carbon atoms), a quaternary ammonium group (which may have 3 to 24 carbon atoms, 3 to 12 carbon atoms, or 3 to 6 carbon atoms), a thiol group, an acyl group (which may have 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms), an acyloxy group (which may have 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms), an aroyl group (which may have 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and particularly preferably 7 to 11 carbon atoms), an aroyloxy group (which may have 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and particularly preferably 7 to 11 carbon atoms), a (meth)acryloyl group, a (meth)acryloyloxy group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group (═O), an imino group (which may have ═NH), an alkylene group (═C(R N ) 2 ) etc. A hetero atom may be interposed in the alkylene chain of the substituent T. The alkyl group, alkenyl group, aryl group, or arylalkyl group possessed by the substituent T may be further substituted by another substituent.

[0097] R N is a hydrogen atom or an organic group. The organic group is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11).

[0098] As examples of specific thermal base generating agents, the compounds shown in Examples can be mentioned.

[0099] In the photosensitive resin composition, the content of the specific thermal base generator is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more in the solid content, and the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.

[0100] The amount is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polymer precursor. The upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.

[0101] By setting the amount within the above range, the effect of the specific thermal base generator can be fully exerted, and the amount of the residual thermal decomposition product can be suppressed to a level that does not affect the reliability of the device, which is preferred.

[0102] The specific thermal base generating agent may be used alone or in combination. When using a plurality of types, the total amount thereof shall be within the above range.

[0103] Furthermore, a specific thermal base generating agent may be used in combination with other thermal base generating agents or may not be used in combination.

[0104] As one embodiment of the present invention, the content of the thermal base generator contained in the photosensitive resin composition of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more.

[0105] <Polymer Precursor>

[0106] The photosensitive resin composition of the present invention contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. The total content of the acid group and the acid generating group contained in the polymer precursor is preferably 0.5 mmol / g or less. As the polymer precursor, a polyimide precursor is more preferred, and a polyimide precursor containing a structural unit represented by the following formula (1) is further preferred.

[0107] <<Polyimide precursor>>

[0108] The polyimide precursor preferably contains a structural unit represented by the following formula (1). By setting it as such a structure, a composition with more excellent film strength can be obtained.

[0109] [Chemical formula 7]

[0110]

[0111] 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 11 3 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. -C(=O)-A 1 -R 114 and -C(=O)-A 2 -R 113 Preferably, they are groups having neither an acid group nor an acid generating group.

[0112] A 1 and A 2 Each is independently an oxygen atom or NH, preferably an oxygen atom.

[0113] R 111 represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, an aromatic heterocyclic 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.

[0114] 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, cycloaliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0115] Specifically, the diamine preferably includes 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 includes an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.

[0116] [Chemical formula 8]

[0117]

[0118] In the formula, A is preferably a single bond or 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 The group selected from -, -NHCO- and combinations thereof is more preferably a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S- and -SO 2 - is further preferably selected from -CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 - and -C(CH 3 ) 2 -a divalent group in the group consisting of

[0119] 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'-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)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 acrylate, 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)] 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. ,

[0120] Furthermore, diamines (DA-1) to (DA-18) shown below are also preferred.

[0121] [Chemical formula 9]

[0122]

[0123] Furthermore, as a preferred example, a diamine having at least two alkylene glycol units in the main chain can also be cited, preferably a diamine containing two or more ethylene glycol chains or propylene glycol chains in total in one molecule, and more preferably a diamine containing 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, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are not limited to these.

[0124] 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.

[0125] [Chemical formula 10]

[0126]

[0127] In the above, x, y, and z are average values.

[0128] 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 of them is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and particularly preferably 6 to 10), 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 these combinations. The definition of the preferred range is the same as that of A in AR-8 above.

[0129] From the perspective of i-ray transmittance, R 111Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred.

[0130] [Chemical formula 11]

[0131]

[0132] 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 them is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

[0133] As R 50 ~R 57 The monovalent organic group may 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).

[0134] [Chemical formula 12]

[0135]

[0136] R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

[0137] 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.

[0138] 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).

[0139] [Chemical formula 13]

[0140]

[0141] R 112 The definition of is the same as that of A in the above AR-8, and the preferred range is also the same.

[0142] Regarding R in formula (1) 115The 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).

[0143] [Chemical formula 14]

[0144]

[0145] R 115 represents a tetravalent organic group. 115 The definition of R is similar to that of formula (1). 115 The definition is the same.

[0146] 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.

[0147] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferred examples.

[0148] [Chemical formula 15]

[0149]

[0150] R in formula (1) 113 and R 114Each independently represents a hydrogen atom or a monovalent organic group. 113 and R 114 At least one of the radical polymerizable groups contains a radical polymerizable group, and more preferably two of the radical polymerizable groups contain a radical polymerizable group. The radical polymerizable group is a group that can undergo a crosslinking reaction by the action of a radical, and a preferred example thereof includes a group having an ethylenically unsaturated bond.

[0151] 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).

[0152] [Chemical formula 16]

[0153]

[0154] In formula (III), R 200 represents a hydrogen atom or a methyl group, and more preferably a methyl group.

[0155] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 - 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; the number of repetitions is preferably 1 to 12 carbon atoms, 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.

[0156] Preferred R 201 Examples of the group include vinyl, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH 2 CH(OH)CH 2 -, more preferably vinyl, propylene, trimethylene, -CH 2 CH(OH)CH 2 -.

[0157] R is particularly preferred 200 is methyl, R 201 For vinyl.

[0158] From the viewpoint of solubility in organic solvents, R 113 or R 114 The monovalent organic group is preferably 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.

[0159] 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 one of a straight chain, a branched chain, or a cyclic chain. Examples of straight chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoryl, dicyclohexyl, and pinenyl. Among them, from the viewpoint of achieving high sensitivity, a cyclohexyl group is most preferred. Furthermore, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred.

[0160] Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.

[0161] Specific examples of the aromatic hydrocarbon group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a condensed pentabenzene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetrabenzene ring, A group having an aromatic hydrocarbon ring such as a chrysene ring, a triphenylene ring, a fluorene ring, or a biphenyl ring.

[0162] Examples of the aromatic heterocyclic group include groups having an aromatic heterocyclic ring such as a substituted or unsubstituted pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianth ring, chromene ring, xanthene ring, phenoxathiine ring, phenothiazine ring or phenazine ring.

[0163] 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 less. The upper limit is not specified, but is actually 50% by mass or less.

[0164] 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.

[0165] It is preferred that the structural unit represented by the formula (1) is a structural unit represented by the formula (1-A).

[0166] [Chemical formula 17]

[0167]

[0168] A 1 , A 2 , R 111 , R 113 and R 114 The definitions of are independent of A in formula (1) 1 , A 2 , R 111 , R 113 and R 114 The definition and preferred range of R are the same. 112 With R in formula (5) 112 The definitions are the same, and the preferred ranges are also the same.

[0169] In the polyimide precursor, the structural unit represented by formula (1) may be one type or two or more types. Furthermore, the structural isomers of the structural unit represented by formula (1) may also be included. Furthermore, the polyimide precursor may include other types of structural units in addition to the structural unit represented by formula (1).

[0170] 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 the total structural units are structural units represented by formula (1). The upper limit is practically 100 mol % or less.

[0171] 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 even more 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 even more preferably 4,000 to 25,000.

[0172] The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0173] 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 halogenated dicarboxylic acid with diamine.

[0174] In the method for producing a polyimide precursor, it is preferred to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds.

[0175] The organic solvent can be appropriately selected according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, and N-ethylpyrrolidone.

[0176] When producing a polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, the solid can be precipitated by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor.

[0177] <<Polybenzoxazole precursor>>>

[0178] The polybenzoxazole precursor preferably includes a structural unit represented by the following formula (2).

[0179] [Chemical formula 18]

[0180]

[0181] 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.

[0182] R 121 The divalent organic group is preferably 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 carbon atoms) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14, and particularly preferably 6 to 12 carbon atoms). 121 The aromatic group includes 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.

[0183] In formula (2), R 122 The tetravalent organic group is defined as R in the above formula (1). 115 The definition is the same, and the preferred range is also the same. 122Preferably, it is derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0184] R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group, and has the same definition as R in the above formula (1). 113 and R 114 The definition of is the same as that of , and the preferred range is also the same. Preferably -OR 124 AND-OR 123 These are groups which do not have an acid group or an acid generating group.

[0185] The polybenzoxazole precursor may contain other types of structural units in addition to the structural unit of the above formula (2).

[0186] From the viewpoint of being able to suppress the warping of the cured film caused by the dead loop, it is preferred that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit.

[0187] [Chemical formula 19]

[0188]

[0189] Z has structure a and structure b, R 1s is 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), which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z portion, preferably structure a is 5 to 95 mol%, structure b is 95 to 5 mol%, and a+b is 100 mol%.

[0190] In formula (SL), preferred examples of Z include R in structure b. 5s and R 6sZ 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 a dehydration dead cycle can be reduced, and the effects of suppressing warpage and improving solubility can be achieved.

[0191] 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 even more 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 even more preferably 4,000 to 25,000.

[0192] The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0193] 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. In addition, 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.

[0194] The photosensitive resin composition of the present invention may contain 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.

[0195] <Solvent>

[0196] 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.

[0197] 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.

[0198] 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.

[0199] As ketones, for example, preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

[0200] As the aromatic hydrocarbons, for example, preferred aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.

[0201] As the sulfoxides, for example, dimethyl sulfoxide is preferably mentioned.

[0202] As the amides, preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0203] 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.

[0204] In the present invention, it is preferred to include 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 of two or more thereof. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously.

[0205] From the viewpoint of coating properties, the content of the solvent is preferably set to an amount such that 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. The content of the solvent can be adjusted according to the desired thickness and coating method.

[0206] The solvent may be contained alone or in combination of two or more. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0207] <Photosensitive agent>

[0208] In the present invention, the photosensitive resin composition contains a photosensitizer. The total content of the acid group and the acid generating group contained in the photosensitizer is preferably 0.5 mmol / g or less. Examples of the photosensitizer include photopolymerization initiators, photocuring accelerators, and sensitizing dyes.

[0209] In the present invention, the total amount of the photosensitizer is preferably 1 to 10% by mass of the photosensitive resin composition, and the photosensitizer is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80 to 100% by mass of the photopolymerization initiator.

[0210] <<Photopolymerization initiator>>

[0211] The photosensitive resin composition used in the present invention may contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0212] The photo-radical polymerization initiator that can be used in the present invention is not particularly limited and can be appropriately selected from known photo-radical polymerization initiators. For example, a photo-radical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, an activator that reacts with a photoexcited sensitizer to generate active free radicals may be used.

[0213] 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 an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0214] The photosensitive resin composition contains a photoradical polymerization initiator, and after the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, curing due to the generated radicals is caused by irradiation with light, thereby reducing the solubility in the light-irradiated portion. Therefore, for example, there is an advantage that by exposing the photosensitive resin composition layer through a photomask having a pattern that shields only the electrode portion, regions with different solubility can be easily produced according to the pattern of the electrode.

[0215] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbimidazoles, 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 the records of paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357, and the content is incorporated into this specification.

[0216] As the ketone compound, for example, the compounds described in paragraph 0087 of JP-A-2015-087611 are exemplified, and the contents are incorporated into the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0217] 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.

[0218] 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 Corporation) can be used.

[0219] 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.

[0220] As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, which have a maximum absorption wavelength that matches a light source having a wavelength of 365 nm or 405 nm, can also be used.

[0221] Examples of the acylphosphine-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.

[0222] Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

[0223] As the photoradical polymerization initiator, oxime compounds are more preferably cited. By using oxime compounds, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as a curing accelerator, so they are particularly preferred.

[0224] 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.

[0225] 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 particularly 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.

[0226] [Chemical formula 20]

[0227]

[0228] 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, photoradical polymerization initiator 2 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 also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also be used.

[0229] Furthermore, oxime compounds having fluorine atoms can also be used. Specific examples of such 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.

[0230] As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

[0231] 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, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0232] More preferred photoradical polymerization initiators are 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. Further preferred are 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. Further preferred are metallocene compounds or oxime compounds, and further preferred are oxime compounds.

[0233] In addition, the photoradical polymerization initiator may also 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-propane-1, quinones formed by ring contraction of 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 also be used.

[0234] [Chemical formula 21]

[0235]

[0236] 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, 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 alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a phenyl or biphenyl group, R I01 is a group represented by formula (II), or is I00 The same group, R I02~R I04 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.

[0237] [Chemical formula 22]

[0238]

[0239] In the formula, R I05 ~R I07 R of the above formula (I) I02 ~R I04 same.

[0240] Furthermore, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used.

[0241] When a photopolymerization initiator is contained, 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 type or two or more types. When two or more photopolymerization initiators are contained, it is preferred that the total amount thereof is within the above range.

[0242] <<Light curing accelerator>>

[0243] The photosensitive resin composition used in the present invention may contain a photocuring accelerator. The photocuring accelerator in the present invention is preferably a photocuring accelerator (photobase generator) that generates a base by exposure, and is a photocuring accelerator that does not show activity under normal conditions of normal temperature and pressure, but is particularly preferably a photocuring accelerator that generates a base (basic substance) when irradiated with electromagnetic waves as an external stimulus. The base generated by exposure acts as a catalyst when the polymer precursor is cured by heating, and therefore can be preferably used.

[0244] In the present invention, a known photocuring accelerator can be used as the photocuring accelerator. Examples thereof include ionic compounds that are neutralized by forming a base component such as a transition metal compound complex, a compound having a structure such as an ammonium salt, a substance that is latent by forming a base with an amidine moiety and a carboxylic acid, and nonionic compounds whose base components are latent by a carbamate bond, an oxime bond, etc., such as carbamate derivatives, oxime ester derivatives, and acyl compounds.

[0245] Examples of the photocuring accelerator of the present invention include a photocuring accelerator having a cinnamic acid amide structure as disclosed in Japanese Unexamined Patent Application Publication No. 2009-080452 and International Publication No. 2009 / 123122, a photocuring accelerator having a carbamate structure as disclosed in Japanese Unexamined Patent Application Publication No. 2006-189591 and Japanese Unexamined Patent Application Publication No. 2008-247747, and a photocuring accelerator having an oxime structure or a carbamoyl oxime structure as disclosed in Japanese Unexamined Patent Application Publication No. 2007-249013 and Japanese Unexamined Patent Application Publication No. 2008-003581, but the present invention is not limited to these, and other structures of known photocuring accelerators can also be used.

[0246] Examples of the photocuring accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP-A-2012-093746, compounds described in paragraphs 0022 to 0069 of JP-A-2013-194205, compounds described in paragraphs 0026 to 0074 of JP-A-2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010 / 064631.

[0247] As commercially available products of the photocuring accelerator, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.

[0248] When a photocuring accelerator is used, the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.

[0249] The photocuring accelerator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

[0250] <<Sensitizing pigment>>

[0251] The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active rays 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. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, and the contents are incorporated into this specification.

[0252] 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 mass %, more preferably 0.1 to 15 mass %, and further preferably 0.5 to 10 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.

[0253] <Thermal radical polymerization initiator>

[0254] The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator within the range not departing from the gist of the present invention.

[0255] Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and start or promote the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of polymer precursors can be carried out together with the cyclization of polymer precursors, thereby achieving a higher degree of heat resistance.

[0256] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

[0257] When a thermal 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 radical polymerization initiator may contain only one or more than one. When two or more thermal radical polymerization initiators are contained, it is preferred that the total amount thereof is within the above range.

[0258] <Polymerizable compounds>

[0259] <<Free Radical Polymerization Compound>>

[0260] The photosensitive resin composition of the present invention preferably contains a radical polymerizable compound.

[0261] The radical polymerizable compound can use a compound having a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl, vinyl, (meth)acryloyl, and allyl. The radical polymerizable group is preferably a (meth)acryloyl group.

[0262] The number of radical polymerizable groups possessed by the radical polymerizable compound may be 1 or 2 or more, but 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.

[0263] 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.

[0264] 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, and more preferably contains 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 refers to the number of free radical polymerizable groups in one molecule.

[0265] As a specific example of a free radical polymerizable compound, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) 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 affinity substituents such as hydroxyl or amino, thiol, etc. and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups 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 halogen 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 unsaturated phosphonic acid, vinylbenzene derivatives 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, and these contents are incorporated into this specification.

[0266] Furthermore, the radical polymerizable monomer 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, neopentyl glycol 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, glycerol or trimethylolethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylate. The present invention also includes the following: the compounds described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193 (meth) acrylic acid urethanes, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490 (polyester acrylates), epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also suitable. In addition, the multifunctional (meth) acrylic acid esters obtained by reacting a multifunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as (meth) acrylic acid glycidyl ester can also be cited.

[0267] Furthermore, as preferred radical polymerizable compounds other than the above, compounds having a fluorene ring and having two or more groups containing an ethylenically unsaturated bond, or cardo resins described in JP-A-2010-160418, JP-A-2010-129825, and JP-4364216 may be used.

[0268] 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, substances introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

[0269] In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can also be preferably used, and the contents are incorporated into the present specification.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] Examples of commercially available radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four vinyloxy 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 oxypentylene chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and NK ester 4G (manufactured by Nippon Paper Industries Co., Ltd.). 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.

[0274] As the radical polymerizable compound, polyurethane acrylates as described in JP-48-041708, JP-51-037193, JP-2-032293, JP-2-016765, and carbamate compounds having an ethylene oxide skeleton as described in JP-58-049860, JP-56-017654, JP-62-039417, JP-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 JP-63-277653, JP-63-260909, JP-1-105238 can also be used.

[0275] From the viewpoint of suppressing the warping caused by the elastic coefficient control of the cured film, the photosensitive resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as a radical polymerizable compound. As a monofunctional 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.

[0276] <<Polymerizable compounds other than the above-mentioned radical polymerizable compounds>>

[0277] The photosensitive resin composition of the present invention may further contain polymerizable compounds other than the above-mentioned radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

[0278] (Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)

[0279] 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.

[0280] [Chemical formula 23]

[0281]

[0282] (wherein, t represents an integer from 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.

[0283] [Chemical formula 24]

[0284]

[0285] (Where 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.

[0286] [Chemical formula 25]

[0287]

[0288] (wherein, 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.

[0289] 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 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

[0290] 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.).

[0291] (Epoxy compound (compound having an epoxy group))

[0292] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C, 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.

[0293] 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.

[0294] Examples of epoxy compounds include 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., but are not limited to these. Specific examples include 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, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, ADEKA CORPORATION), etc. Among these, epoxy resins containing polyethylene oxide groups are preferred from the perspective of suppressing warping 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.

[0295] (Oxetane compound (compound having an oxetane group))

[0296] 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 a specific example, 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.

[0297] (Benzoxazine compound (compound having a benzoxazolyl group))

[0298] 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.

[0299] 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.

[0300] 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 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

[0301] The polymerizable compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount is preferably within the above range.

[0302] <Migration inhibitor>

[0303] 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 from the metal layer (metal wiring) into the photosensitive resin composition layer.

[0304] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and mercapto groups, 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.

[0305] Furthermore, an ion capture agent that captures anions such as halogen ions may also be used.

[0306] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, and the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520 can be used.

[0307] Specific examples of the migration inhibitor include the following compounds.

[0308] [Chemical formula 26]

[0309]

[0310] 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 even more preferably 0.1 to 1.0% by mass based on the total solid content of the photosensitive resin composition.

[0311] The migration inhibitor may be one type or two or more types. When the migration inhibitor is two or more types, the total amount thereof is preferably within the above range.

[0312] <Polymerization inhibitor>

[0313] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

[0314] As the polymerization inhibitor, for example, hydroquinone, 4-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-phenylnaphthalene can be preferably used. Amine, 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 inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015 / 125469 can also be used.

[0315] Furthermore, the following compounds (Me is methyl group) can also be used.

[0316] [Chemical formula 27]

[0317]

[0318] When the photosensitive resin composition of the present invention has 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.

[0319] The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

[0320] <Metal Adhesion Improver>

[0321] 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.

[0322] Examples of silane coupling agents include 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. 2011 / 080992, 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. 2014 / 097594. In addition, 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. In addition, the silane coupling agent is also preferably the following compound. In the following formula, Et represents an ethyl group.

[0323] [Chemical formula 28]

[0324]

[0325] Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfides described in paragraphs 0032 to 0043 of JP-A-2013-072935 can be used.

[0326] 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.

[0327] <Other additives>

[0328] The photosensitive resin composition of the present invention can be added with various additives as needed within the range that does not impair the effects of the present invention, such as chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are added, it is preferred that the total amount added is set to 3% by mass or less of the solid content of the composition.

[0329] <<Chain transfer agent>>

[0330] 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 (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

[0331] When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass relative to 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, it is preferred that the total range is the above range.

[0332] <<Surfactant>>

[0333] From the viewpoint of improving coating properties, various surfactants can be added to the photosensitive resin composition of the present invention. As surfactants, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used. In addition, the following surfactants are also preferred.

[0334] [Chemical formula 29]

[0335]

[0336] 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 % relative to the total solid content of the photosensitive resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one or two or more. When there are two or more surfactants, it is preferred that the total range is within the above range.

[0337] <<Higher fatty acid derivatives>>

[0338] 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 as to be locally present on the surface of the composition during the drying process after coating.

[0339] When the photosensitive resin composition of the present invention has 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 within the above range.

[0340] <Regulation on other contained substances>

[0341] 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 %.

[0342] 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, and nickel. When multiple metals are included, the total amount of these metals is preferably within the above range.

[0343] In addition, as a method for reducing metal impurities unintentionally 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.

[0344] Considering the use as a semiconductor material, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the substance existing in the state 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 listed. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably in the above ranges, respectively.

[0345] As the storage container for 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 Laid-Open No. 2015-123351.

[0346] <Preparation of Composition>

[0347] 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.

[0348] 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 using multiple filters, 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 circulating filtration. Furthermore, filtering can be performed after pressurization. When filtering after pressurization, it is preferred that the pressure for pressurization is greater than 0.05 MPa and less than 0.3 MPa.

[0349] 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.

[0350] In the present invention, the total content of the acid groups and acid generating groups contained in the polymer precursor and the photosensitive agent in the photosensitive resin composition (the amount of acid groups, etc. [ΣAc]) is 0.5 mmol / g or less. The acid groups in this specification are groups having a pKa of 4 or less, and examples thereof include carboxylic acids and sulfonic acids. The acid generating groups in this specification are groups that can generate acid groups in the liquid of the photosensitive resin composition or in the film obtained from the photosensitive resin composition by a process using the photosensitive resin composition such as heating and exposure, and examples thereof include groups in which the above-mentioned acid groups are protected by desorption, etc.

[0351] The amount of acid groups in the photosensitive resin composition of the present invention is preferably 0.4 mmol / g or less, more preferably 0.3 mmol / g or less, and further preferably 0.2 mmol / g or less. As a lower limit, it is actually 0.01 mmol / g or more. In the present invention, the amount of the acid groups is suppressed to a very low level, so that good development can be performed by an organic solvent without the aid of an alkaline solution. In addition, it is speculated that the resin composition in the above-mentioned patent document 1 is alkali-soluble, so (for example

[0064] ), the amount of acid groups in the resin exceeds 2.0 mmol / g.

[0352] <Cured film, laminate, semiconductor device, and method for producing the same>

[0353] Next, a cured film, a laminated body, a semiconductor device, and methods for producing these will be described.

[0354] 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.

[0355] The cured film of the present invention may be stacked in two or more layers to form a laminate, and may be stacked in 3 to 7 layers to form a laminate. The laminate having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

[0356] 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, the use of molded parts in etching, and the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0357] 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 includes a film forming step (a layer forming step in which the photosensitive resin composition of the present invention is applied to a substrate to form a film) and a heating step in which the photosensitive resin composition in a layer is heated at 80 to 450°C (preferably 80 to 350°C). The method for producing a cured film preferably includes a production method having the following steps: an exposure step in which the film is exposed after the above-mentioned film forming step (layer forming step); and a developing step in which the above-mentioned exposed photosensitive resin composition layer (film, i.e., resin layer) is developed. After the development, a heating step of heating (preferably heating at 80 to 450°C) (more preferably 80 to 350°C) is included, thereby further curing the exposed resin layer. In addition, as described above, when using a photosensitive resin composition, the composition is cured by exposure in advance, and then the desired processing (such as the following lamination) is performed as needed, thereby further curing it by heating.

[0358] The method for manufacturing a laminate of the present invention includes the method for manufacturing a cured film of the present invention. The method for manufacturing a laminate of the present invention is according to the method for manufacturing the cured film described above. After forming a cured film, the film forming step (layer forming step) and the heating step of the photosensitive resin composition are further performed again or photosensitivity is imparted. It is preferred to perform the film forming step (layer forming step), the exposure step and the developing step (if necessary, there is a further heating step) in the above order. In particular, it is preferred to perform the above steps multiple times (more than 2 layers) or 3 to 7 times (i.e., 3 to 7 layers) in sequence. By stacking the cured films in this way, a laminate can be made. In the present invention, it is particularly preferred to provide a metal layer on a portion where a cured film is provided or between the cured films or between the two.

[0359] These will be described in detail below.

[0360] <<Film forming step (layer forming step)>>

[0361] 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).

[0362] The type of substrate can be appropriately determined according to the purpose, and is not particularly limited to semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, electrode plate of plasma display device (PDP), etc. In the present invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates are more preferred.

[0363] 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.

[0364] As a method of applying the photosensitive resin composition to a substrate, coating is preferred.

[0365] Specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet are exemplified as applicable methods. 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 and coating conditions are adjusted to obtain a resin layer of the desired thickness. In addition, the coating method can also be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, it is preferably a spin coating method or a spray coating method, an inkjet method, etc. If it is a rectangular substrate, it is preferably a slit coating method or a spray coating method, an inkjet method, etc. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

[0366] <<Drying process>>

[0367] The manufacturing method of the present invention may also 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.

[0368] <<Exposure process>>

[0369] The manufacturing method of the present invention may also include an exposure step of exposing the photosensitive resin composition layer. The exposure amount is not particularly limited as long as it can cure the photosensitive resin composition. For example, it is preferably irradiated with 100 to 10000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably irradiation 200 to 8000 mJ / cm2 .

[0370] The exposure wavelength can be appropriately determined within the range of 190 to 1000 nm, and is preferably 240 to 550 nm.

[0371] In terms of the relationship with the light source, the exposure wavelength can be (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide band (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the photosensitive resin composition of the present invention, it is particularly preferred to be exposed by a high pressure mercury lamp, and among them, it is preferred to be exposed by i-ray. In this way, a particularly high exposure sensitivity can be obtained.

[0372] <<Development process>>

[0373] The manufacturing method of the present invention may include a developing step of developing the exposed photosensitive resin composition layer. The unexposed portion (non-exposed portion) is removed by developing. The developing method is not particularly limited as long as the desired pattern can be formed, and for example, a developing method such as coating, spraying, dipping, or ultrasonic wave can be used.

[0374] Development is carried out using a developer. The 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 more preferably the developer contains 90% by mass 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.

[0375] As the organic solvent, preferably 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 propionic acid alkyl esters (e.g., 3-alkoxy propionic acid methyl ester, 3-alkoxy propionic acid ethyl ester, etc. (e.g., 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (e.g., 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester, etc. (e.g., 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid propyl ester, etc.) ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosol acetate, ethyl As base fiber solvents, for example, 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.; and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be preferably listed; and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably listed; as sulfoxides, dimethyl sulfoxide can be preferably listed.

[0376] In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

[0377] 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. The developer may also contain 100% by mass of an organic solvent.

[0378] The developer is preferably a non-alkaline developer. From this point of view, it is preferred that the developer containing the above-mentioned organic solvent as the main body does not contain an alkaline compound. For example, as described in

[0064] of Patent Document 1, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. can be removed from the preferred developer used in the present invention.

[0379] 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.

[0380] After the treatment with the developer, the photosensitive resin composition may be further rinsed. Preferably, the rinse is performed using a solvent different from the developer. For example, the rinse may be performed using a solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

[0381] <<Heating process>>

[0382] The manufacturing method of the present invention preferably includes a film forming step (layer forming step), a drying step or a heating step after 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, but the curing of the free radical polymerizable compound other than the unreacted polymer precursor can also be carried out in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or more, more preferably 80°C or more, further preferably 140°C or more, further preferably 160°C or more, and further preferably 170°C or more. As an 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.

[0383] Regarding heating, the temperature at the start of heating to the maximum heating temperature is preferably carried out at a heating rate of 1 to 12°C / min, 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, productivity can be ensured while preventing excessive volatilization of amines, and by setting the heating rate to 12°C / min or less, residual stress in the cured film can be relaxed.

[0384] 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 refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is preferably gradually increased from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition.

[0385] The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

[0386] In particular, when a multilayer laminate is formed, from the viewpoint of the adhesion between the layers of the cured film, the heating temperature is preferably 180° C. to 320° C., and more preferably 180° C. to 260° C. The reason for this is not clear, but it is considered that this is because the acetylene groups of the polymer precursors between the layers undergo a cross-linking reaction.

[0387] Heating can be performed in stages. As an example, the following pretreatment process can be performed: heating from 25°C to 180°C at 3°C / min, 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. As the heating temperature of the pretreatment process, it is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In this pretreatment process, as described in the gazette of U.S. Patent No. 9159547, it is also preferred to treat while irradiating ultraviolet rays. By this pretreatment process, the properties of the film can be improved. The pretreatment process can be performed in a shorter time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be set as a step of more than two stages, for example, pretreatment process 1 is performed in the range of 100-150°C, and then pretreatment process 2 is performed in the range of 150-200°C.

[0388] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[0389] In order to prevent decomposition of the polymer precursor, the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[0390] <<Metal layer forming process>>

[0391] 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.

[0392] The metal layer is not particularly limited, and existing metals 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.

[0393] The formation method of the metal layer is not particularly limited, and existing methods can be adopted. 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, electroplating, electroless plating, etching, printing, and the method of combining these can be considered. More specifically, the patterning method combining sputtering, photolithography and etching, and the patterning method combining photolithography and electroplating can be listed.

[0394] The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, based on the thickest portion.

[0395] <<Lamination process>>

[0396] The production method of the present invention preferably further includes a lamination step.

[0397] The lamination process refers to a series of processes of performing the above-mentioned film formation process (layer formation process) and heating process again on the surface of the cured film (resin layer) or the metal layer, or performing the above-mentioned film formation process (layer formation process), the above-mentioned exposure process and the above-mentioned development process in the photosensitive resin composition in the above-mentioned order. Of course, the lamination process may also include the above-mentioned drying process and heating process, etc.

[0398] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment is exemplified.

[0399] The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

[0400] For example, the resin layer preferably has a structure of 3 to 7 layers, more preferably 3 to 5 layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer.

[0401] That is, in the present invention, it is particularly preferred that after the metal layer is provided, the film forming step (layer forming step) and the heating step of the photosensitive resin composition are further performed to cover the metal layer, or the film forming step (layer forming step), the exposure step and the development step (if necessary, the heating step) are performed in the photosensitive resin composition in the above order. By alternately performing the lamination step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

[0402] The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description of FIG. 1 , and these contents are incorporated into this specification.

[0403] In addition, the sealing film, substrate material (base film and cover film of flexible printed substrate, interlayer insulating film) or insulating film for mounting purposes as above can be patterned by etching, etc. For the use of these, for example, reference can be made to Science&technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, edited by Masaaki Kakimoto, CMC Technical library "Basics and Development of Polyimide Materials" November 2011, Japan Polyimide Aromatic Polymer Research Association "Latest Polyimide Basics and Applications" NTS Inc, August 2010, etc.

[0404] Example

[0405] Hereinafter, the present invention will be further described in detail by enumerating examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the scope of the purpose of the present invention. Thus, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are mass references unless otherwise specified.

[0406] <Synthesis of polymer precursor (resin)>

[0407] <Synthesis example 1>

[0408] [Synthesis of Polyimide Precursor A-1 Derived from 4,4'-oxydiphthalic Dianhydride, 2-Hydroxyethyl Methacrylate and 4,4'-Diaminodiphenyl Ether]

[0409] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 1 mg of water, and 250 mL of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 4 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. The water content of the obtained reaction solution was measured and found to contain 133 mass ppm. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl was added over 60 minutes while the temperature was maintained at -10°C. 2. After diluting with 50 mL of N-methylpyrrolidone, a solution of 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone and added dropwise to the reaction mixture at -10°C for 60 minutes. After stirring the mixture for 2 hours, 20 mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was precipitated into a polyimide precursor in 6 liters of water and filtered, and dried at 45°C for 3 days under reduced pressure to obtain a solid powder of the polyimide precursor. The weight average molecular weight of the polyimide precursor A-1 is 23,300, and the number average molecular weight is 9,600.

[0410] <Synthesis example 2>

[0411] [Synthesis of Polyimide Precursor A-2 Derived from 4,4'-oxydiphthalic Dianhydride, 2-Hydroxyethyl Methacrylate and the Diamine (a) Shown Below]

[0412] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 1 mg of water, and 250 mL of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 4 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. The water content of the obtained reaction solution was measured and found to contain 120 mass ppm. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl was added over 60 minutes while the temperature was maintained at -10°C. 2 . After diluting with 50 mL of N-methylpyrrolidone, 38.0 g of the solution of the hydroxyl-containing diamine (a) shown below was dissolved in 100 mL of N-methylpyrrolidone, and the solution was added dropwise to the reaction mixture at -10°C for 60 minutes. After stirring the mixture for 2 hours, 20 mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was precipitated into a polyimide precursor in 6 liters of water and filtered, and dried at 45°C for 3 days under reduced pressure to obtain a solid powder of the polyimide precursor. The weight average molecular weight of the polyimide precursor A-2 is 29400, the number average molecular weight is 10800, and the acid value is 5.6 mgKOH / g.

[0413] Diamine (a)

[0414] [Chemical formula 30]

[0415]

[0416] <Synthesis example 3>

[0417] [Synthesis of Polyimide Precursor A-3 Derived from 4,4'-Oxydiphthalic Dianhydride, 2-Hydroxyethyl Methacrylate and 4,4'-Diaminodiphenyl Ether]

[0418] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 1 mg of water, and 250 mL of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 4 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. The water content of the obtained reaction solution was measured and found to contain 1450 mass ppm. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl was added over 60 minutes while the temperature was maintained at -10°C. 2 . After diluting with 50 mL of N-methylpyrrolidone, a solution of 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone and added dropwise to the reaction mixture at -10°C for 60 minutes. After stirring the mixture for 2 hours, 20 mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was precipitated into a polyimide precursor in 6 liters of water and filtered, and dried at 45°C for 3 days under reduced pressure to obtain a solid powder of the polyimide precursor. The weight average molecular weight of the polyimide precursor A-3 is 22,000, and the number average molecular weight is 10,000.

[0419] <Synthesis example 4>

[0420] [Synthesis of a polyimide precursor composition A-4 derived from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

[0421] 42.4 g of 4,4'-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at 60°C for 4 hours. Next, the reaction mixture was cooled to -10°C, and a solution of 34.35 g of diisopropylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture was stirred for 30 minutes. Next, a solution of 25.1 g of 4,4'-diaminodiphenyl ether dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture was stirred for 1 hour. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was precipitated with a polyimide precursor in 14 L of water and filtered, and dried at 45°C for 2 days under reduced pressure. The obtained powdery polyimide precursor A-4 had a weight average molecular weight of 23,800 and a number average molecular weight of 8,700.

[0422] <Synthesis Example 5>

[0423] [Synthesis of Polybenzoxazole Precursor A-5 Derived from 4,4'-Carbonyldibenzoic Acid, 2,2'-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane and Methacryloyl Chloride]

[0424] 18.5 g of 4,4'-carbonyldibenzoic acid and 250 mL of N-methylpyrrolidone were mixed. Then, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl was added over 60 minutes while maintaining the temperature at -10±5°C. 2. Then, a solution of 21.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -10±5°C over 60 minutes, and the mixture was stirred for 2 hours. Then, 9.3 g of triethylamine was added to the obtained reaction solution under ice-cold conditions, 12.0 g of methacryloyl chloride was added dropwise, and the mixture was further stirred under ice-cold conditions for 2 hours to obtain a solution containing a polybenzoxazole precursor. Then, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The solid polybenzoxazole precursor was filtered out and dissolved in 380 g of tetrahydrofuran. The obtained solution was added to 6 liters of water, the polybenzoxazole precursor was precipitated, and the water-polybenzoxazole precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The solid polybenzoxazole precursor was filtered out again and dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor A-5 was 28,900 and the number average molecular weight was 8,800. The proportion of components with a molecular weight of 1,000 or less was 0.3% by mass.

[0425] <Preparation of photosensitive resin composition>

[0426] The polymer precursor was mixed with the components listed in Table 1 below to form a uniform solution, thereby preparing a coating solution of a photosensitive resin composition. Each photosensitive resin composition was passed through a filter having a pore width of 0.8 μm manufactured by ADVANTEC CO., LTD., and was filtered under pressure.

[0427] <Temperature at which alkali is generated>

[0428] 3.0 mg of the polymer precursor was weighed and measured using TGA (TA Instruments, Q500 model) with the temperature at which the mass was reduced by 5% when the temperature was raised to 500°C at a rate of 20°C / min as the base generation temperature from the thermal base generator. In addition, the pKa of the conjugate acid of the generated base was determined by identifying the decomposition species using LC-MS and calculating the pKa of the structure of the conjugate acid of the decomposition species obtained using the following software package. Software package: Advanced Chemistry Development (ACD / Labs) software V8.14 supporting Solaris system (1994-2007 ACD / Labs)

[0429] <Amount of acid groups, etc.>

[0430] For each photosensitive resin composition in Examples and Comparative Examples, the total content of the acid group and the acid generator contained in the photosensitive agent (amount of acid group, etc.: ΣAc [mmol / g]) was measured by NMR (nuclear magnetic resonance) method.

[0431] <Storage stability>

[0432] Each photosensitive resin composition was left at room temperature (25° C.) and the storage stability was evaluated for a period of time until precipitates could be visually observed.

[0433] A: No precipitation was observed even after 2 weeks.

[0434] B: Precipitation was observed within 1 week and 2 weeks.

[0435] C: Precipitation was observed within 1 week.

[0436] D: Incompatible substances were found during the preparation stage.

[0437] <Mechanical properties (tensile strength)>

[0438] Each photosensitive resin composition was applied to a silicon wafer by spin coating to form a photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100° C. for 4 minutes to form a photosensitive resin composition layer with a uniform thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed to light at 400 mJ / cm using a broadband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01). 2 The exposed photosensitive resin composition layer (resin layer) was exposed at an exposure energy of 5°C / min in a nitrogen atmosphere, and after reaching 230°C, it was heated for 3 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film.

[0439] The resin film peeled from the silicon wafer was subjected to a tensile strength test. In the test, a tensile force tester (Tensilon) was used, with a crosshead speed of 300 mm / min, a width of 10 mm, and a sample length of 50 mm. The film was measured in the long side and width direction at 25°C and 65% RH (relative humidity) in accordance with JIS-K6251 (Japanese Industrial Standard). For evaluation, the elongation at break when cut was measured 10 times, and the average value was used. The results were differentiated and evaluated as follows.

[0440] A: More than 60%

[0441] B: 50% or more and less than 60%

[0442] C: less than 50%

[0443] <Solubility of developer in unexposed area>

[0444] Each photosensitive resin composition was applied to a silicon wafer by spin coating. The silicon wafer to which the photosensitive resin composition was applied was heated by a 100°C hot plate for 4 minutes to obtain a photosensitive resin composition layer with a thickness of 20 μm. The above-mentioned photosensitive resin composition layer was immersed in cyclopentanone at 23°C, and the time required for complete dissolution was measured, thereby calculating the dissolution rate. In the test, a resist development analyzer (RDA-790EB manufactured by Litho Tech Japan Corporation) was used. The results were differentiated and evaluated as follows.

[0445] A: 0.55 μm / second or more

[0446] B: 0.4 μm / second or more and less than 0.55 μm / second

[0447] C: less than 0.4 μm / second

[0448] <Photolithography>

[0449] Each photosensitive resin composition was applied to a silicon wafer by spin coating. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100°C for 4 minutes to form a photosensitive resin composition layer with a thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005i9C). The exposure was performed using i-rays at a wavelength of 365 nm at 200, 300, 400, 500, 600, 700, and 800 mJ / cm 2 Exposure was performed from 5 μm to 25 μm at each exposure energy using a line and space photomask with 1 μm increments.

[0450] The exposed photosensitive resin composition layer was negatively developed for 60 seconds using cyclopentanone. The smaller the line width of the obtained photosensitive resin composition layer (pattern), the greater the difference in solubility between the light-irradiated part and the light-non-irradiated part in the developer, which is a preferred result. In addition, for changes in exposure energy, if the change in line width is small, it means that the exposure latitude is large, which is a preferred result. The measurement limit is 5μm. The results were differentiated and evaluated as follows.

[0451] A: 10μm or less

[0452] B: more than 10μm and less than 20μm

[0453] C: A pattern exceeding 20 μm or having a line width with edge sharpness could not be obtained.

[0454]

[0455] <Photopolymerization initiator (photosensitive agent)>

[0456] IRGACURE OXE01 (trade name) manufactured by BASF

[0457] IRGACURE784 (trade name) manufactured by BASF

[0458] IRGACURE OXE01 / IRGACURE784 (both trade names) manufactured by BASF

[0459] Mixing ratio 1 / 1 (mass ratio)

[0460] ΣAc: Total content of acid groups and acid-generating groups in polymer precursor and photosensitizer [mmol / g]

[0461] <Radical polymerizable compound (polymerizable compound)>

[0462] SR-209 (trade name) [2-functional] Made by ArKema SA

[0463] A-TMMT (trade name) [4-functional] manufactured by Shin Nakamura Chemical Co., Ltd.

[0464] DPHA (trade name) [6 functionalities] Made by Nippon Kayaku Co., Ltd.

[0465] <Solvent>

[0466] NMP(N-methylpyrrolidone) / ethyl lactate

[0467] BGL (γ-butyrolactone) / DMSO (dimethyl sulfoxide)

[0468] Mixing ratio 200 / 100 (mass ratio)

[0469] <Thermal alkali generator>

[0470] [Chemical formula 31]

[0471]

[0472] TBG1:

[0473] pKa 32, base generation temperature 180°C, pKa of the conjugate acid of the generated base 11.4, molar absorption coefficient 40l / (mol·cm)

[0474] TBG2:

[0475] pKa 4, base generation temperature 150°C, pKa 5.1 of the conjugate acid of the generated base, molar absorption coefficient 0l / (mol·cm)

[0476] TBG3:

[0477] pKa 30, base generation temperature 200°C, pKa of the conjugate acid of the generated base 11.4, molar absorption coefficient 20l / (mol·cm)

[0478] TBG4:

[0479] pKa 16.2, base generation temperature 170°C, pKa of the conjugate acid of the generated base 11.4, molar absorption coefficient 10l / (mol·cm)

[0480] TBG5:

[0481] pKa30, base generation temperature 160°C, pKa9 of the conjugate acid of the generated base, molar absorption coefficient 0l / (mol·cm)

[0482] TBG6:

[0483] pKa 32, base generation temperature 190°C, pKa of the conjugate acid of the generated base 10.4, molar absorption coefficient 0l / (mol·cm)

[0484] The above results show that the photosensitive resin composition using a specific thermal base generator in the present invention shows good results (B or more) in terms of storage stability, mechanical properties, developer solubility in the unexposed part, and photolithography, and is generally excellent. On the other hand, when a thermal base generator (TBG2) having a tertiary amine structure and a carboxyl group is used (Comparative Example 1), the storage stability is poor. When no thermal base generator is used (Comparative Example 2), the mechanical properties are poor. When a polymer precursor with a high acid value is used (Comparative Example 3), the storage stability, developer solubility in the unexposed part, and photolithography are poor.

[0485] <Example 100>

[0486] The photosensitive resin composition of Example 1 was filtered under pressure through a filter having a pore width of 0.8 μm, and then applied to a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100° C. for 5 minutes, and a photosensitive resin composition layer having a uniform thickness of 15 μm was formed on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was subjected to a 500 mJ / cm 2The exposed photosensitive resin composition layer (resin layer) was exposed with an exposure energy of 100 μm, and the exposed photosensitive resin composition layer (resin layer) was developed with cyclopentanone for 60 seconds, thereby forming a hole (patterning) with a diameter of 10 μm. Next, the temperature was increased at a heating rate of 10°C / min in a nitrogen atmosphere, and after reaching 250°C, it was maintained at this temperature for 3 hours. After cooling to room temperature, a thin copper layer (metal layer) with a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by a vapor deposition method in a manner covering the above-mentioned hole portion. Furthermore, the same type of photosensitive resin composition was used again on the surface of the metal layer and the photosensitive resin composition layer, and the sequence from filtering the photosensitive resin composition to heating the patterned film for 3 hours was implemented again in the same manner as above, thereby producing a laminate consisting of a resin layer / metal layer / resin layer.

[0487] This resin layer (interlayer insulating film for redistribution layer) has excellent insulating properties.

[0488] Furthermore, a semiconductor device was manufactured using the interlayer insulating film for redistribution layer, and it was confirmed that the device operated normally.

Claims

1. A photosensitive resin composition comprising: At least one thermal base generating agent selected from the group consisting of a thermal base generating agent represented by the following formula (B1-1) and a thermal base generating agent represented by the following formula (B1-2); At least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and Photosensitive agent, The total content of the acid groups and acid generating groups contained in the polymer precursor and the photosensitizer is 0.5 mmol / g or less; In formula (B1-1) and (B1-2), R 11 and R 12 is a cycloalkyl group, R 31 and R 32 is a cycloalkyl group, R 13 is alkyl, alkenyl, aryl or arylalkyl, R 33 and R 34 are independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an arylalkyl group, R 35 is an alkyl, alkenyl, aryl or arylalkyl group, wherein R 11 , R 12 , R 13 , R 31 , R 32 , R 33 , R 34 and R 35 It does not have a carboxyl group.

2. The photosensitive resin composition according to claim 1, wherein The alkali generation temperature of the thermal alkali generator is 120° C. or higher and 200° C. or lower.

3. The photosensitive resin composition according to claim 1 or 2, wherein The pKa of the thermal base generator is greater than 7.

4. The photosensitive resin composition according to claim 1 or 2, wherein The polymer precursor includes a polyimide precursor.

5. The photosensitive resin composition according to claim 4, wherein The polyimide precursor is 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.

6. The photosensitive resin composition according to claim 1 or 2, wherein The molar absorption coefficient of the thermal base generator at a wavelength of 365 nm is 100 l / (mol·cm) or less.

7. The photosensitive resin composition according to claim 1 or 2, wherein The thermal base generator includes a thermal base generator that generates a base having a conjugate acid with a pKa of 10 or more by heating.

8. The photosensitive resin composition according to claim 1 or 2, wherein The photosensitizer contains a photopolymerization initiator. 9 . The photosensitive resin composition according to claim 1 , which is used for development using a developer containing 90% by mass or more of an organic solvent. 10 . The photosensitive resin composition according to claim 1 , which is used for forming an interlayer insulating film for a redistribution layer. 11 . A cured film obtained by curing the photosensitive resin composition according to claim 1 . 12 . The cured film according to claim 11 , which has a film thickness of 1 μm to 30 μm. 13 . A laminate comprising two or more layers of the cured film according to claim 11 or 12. 14 . A laminate comprising 3 to 7 or more layers of the cured film according to claim 11 or 12.

15. The laminate according to claim 13, wherein There is a metal layer between the cured films.

16. A method for producing a cured film, comprising: A film forming step of applying the photosensitive resin composition according to any one of claims 1 to 10 to a substrate to form a film. 17 . The method for producing a cured film according to claim 16 , comprising an exposure step of exposing the film to light and a development step of developing the film.

18. The method for producing a cured film according to claim 17, wherein: The developer used in the development contains 90% by mass or more of an organic solvent.

19. The method for producing a cured film according to claim 16, comprising: A step of heating the film at 80°C to 450°C. 20 . A method for producing a laminated body, comprising performing the method for producing a cured film according to claim 16 a plurality of times. 21 . A semiconductor device comprising the cured film according to claim 11 or 12 or the laminated body according to any one of claims 13 to 15.

22. A thermal base generating agent represented by the following formula (B1-2): In formula (B1-2), R 31 and R 32 is a cycloalkyl group, R 33 and R 34 are independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an arylalkyl group, R 35 is an alkyl, alkenyl, aryl or arylalkyl group, wherein R 31 , R 32 , R 33 , R 34 and R 35 It does not have a carboxyl group. 23 . The thermal base generator according to claim 22 , which is used for a photosensitive resin composition developed using a developer containing 90% by mass or more of an organic solvent.

24. Use of a thermal alkali generator, which is the use of a thermal alkali generator represented by the following formula (B1-1), The thermal alkali generator is used for a photosensitive resin composition developed using a developer containing 90% by mass or more of an organic solvent. In formula (B1-1), R 11 and R 12 is a cycloalkyl group, R 13 is an alkyl, alkenyl, aryl or arylalkyl group, wherein R 11 , R 12 and R 13 It does not have a carboxyl group.

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