Photosensitive resin composition containing low dielectric loss tangent agent

Abstract

To provide a photosensitive resin composition which exhibits a low dielectric loss tangent, is excellent in storage stability, and enables formation of a cured relief pattern with high resolution, a method for producing polyimide and a method for producing a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.SOLUTION: A photosensitive resin composition contains 100 pts.mass of (A) a polyimide precursor, 0.1-10 pts.mass of (B) a photosensitive agent, 1-50 pts.mass of (C) a low dielectric loss tangent agent, and 50-300 pts.mass of (D) a solvent, in which (C) the low dielectric loss tangent agent has a molecular weight of 100-3,500.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition containing a low dielectric tangent agent, such as a negative photosensitive resin composition used for forming an insulating material for electronic components, and a relief pattern of a passivation film, a buffer coat film, an interlayer insulating film, or the like in a semiconductor device, a method for producing a polyimide using the same, a method for producing a cured relief pattern, and a semiconductor device. [Background technology]

[0002] Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used as insulating materials for electronic components, and passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant relief pattern film by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment by curing it. Such photosensitive polyimide precursor compositions have the characteristic of enabling a significant reduction in the process compared to conventional non-photosensitive polyimide materials.

[0003] Incidentally, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to the purpose. Conventional elements were generally fabricated by a wire bonding method in which thin wires connect the external terminals (pads) of the element to a lead frame. However, today, as elements have become faster and their operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to precisely control the length of the mounting wiring, and it has become difficult to meet this requirement using wire bonding.

[0004] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and directly mounted on a printed circuit board. This flip-chip mounting allows accurate control of the wiring distance, and is therefore adopted for high-end devices that handle high-speed signals, and for mobile phones and the like due to the small mounting size, and demand is rapidly expanding. More recently, a semiconductor chip mounting technology called fan-out wafer level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a wafer that has undergone pre-processing, the individual chips are reconstructed on a support, sealed with molding resin, and a rewiring layer is formed after the support is peeled off (for example, Patent Document 1). The fan-out wafer level packaging has the advantage of being able to reduce the height of the package, as well as enabling high-speed transmission or low cost. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2005-167191 A Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, there has been an urgent need to develop packages for the fifth generation mobile communication system (5G), a new communication standard. 5G uses the millimeter wave (10 GHz to 80 GHz) frequency band, which enables high speed and large capacity, low signal latency, and simultaneous connection of multiple terminals, which were not possible with conventional communications. On the other hand, it is known that the dielectric tangent (tan δ) of insulating materials is high in high frequency ranges such as millimeter waves, causing transmission loss. In order to reduce transmission loss, antenna-in-package (AiP) has been developed, in which the front-end module (FEM) that transmits and receives radio waves and the antenna are integrated. However, the dielectric tangent of insulating materials has a large effect on transmission loss, so materials with low dielectric tangent are required.

[0007] Therefore, an object of the present invention is to provide a photosensitive resin composition that exhibits a low dielectric tangent, has excellent storage stability, and is capable of forming a cured relief pattern with high resolution, a method for producing a polyimide using the photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device having the cured relief pattern. [Means for solving the problem]

[0008] The present inventors have found that the above object can be achieved by combining a polyimide precursor with an agent for reducing dielectric tangent, and have completed the present invention. [1] (A) polyimide precursor: 100 parts by mass, (B) photosensitizer: 0.1 to 10 parts by mass, (C) low dielectric tangent agent: 1 to 50 parts by mass, and (D) Solvent: 50 to 300 parts by mass wherein the (C) agent for reducing dielectric tangent has a molecular weight of 100 to 3,500. [2] The (C) dielectric loss tangent reducing agent is represented by the following formula (I): [ka] {In the formula, R1, R4, and R5 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2 and R3 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms; and Z is an organic group having 7 to 80 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or an organic group having 2 to 15 carbon atoms and containing a carbonyl group.} Item 2. The photosensitive resin composition according to item 1, having a structure represented by the following formula: [3] The (C) dielectric loss tangent reducing agent is represented by the following formula (II): [ka] {wherein R1, R4, R5, R6, R7, and R10 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2, R3, R8, and R9 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms; and Z is a divalent organic group having 1 to 50 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a divalent organic group having 1 to 75 carbon atoms.} 3. The photosensitive resin composition according to item 1 or 2, having a structure represented by the following formula: [4] The (C) dielectric loss tangent reducing agent is represented by the following formula (III): [ka] {wherein R1, R4, R5, R6, R9, and R 10 and R 11 and R 12 and R 15 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2, R3, R8, R7, and R 13 and R 14 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms, and Z is a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.} 3. The photosensitive resin composition according to item 1 or 2, having a structure represented by the following formula: [5] 5. The photosensitive resin composition according to any one of items 2 to 4, wherein Z has at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen. [6] (C) The low dielectric tangent agent has the following formula: [ka] {In the formula, Z is an organic group containing a carbonyl group and having 2 to 15 carbon atoms.} 3. The photosensitive resin composition according to item 1 or 2, having at least one structure represented by the following formula: [7] The (C) dielectric loss tangent reducing agent is represented by the following formula (IV): [ka] {wherein R1, R4, R5, R6, R7, and R 10 and R 11 and R 12 and R 15 and R 16 and R 19 and R 20 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2, R3, R8, R9, and R 13 and R 14 and R 17 and R 18 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 50 carbon atoms, and Z is a tetravalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a tetravalent organic group having 1 to 50 carbon atoms.} 3. The photosensitive resin composition according to item 1 or 2, having a structure represented by the following formula: [8] The polyimide precursor (A) is represented by the following general formula (1): [ka] In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is represented by the following general formula (2): [ka] (In formula (2), R3, R4, and R5 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.) It is a group represented by the following formula: 8. The photosensitive resin composition according to any one of items 1 to 7, wherein the photosensitive resin composition is represented by the following formula: [9] The Y1 is represented by the following formula (Y1): [ka] In the formula, Rz each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, A represents an oxygen atom or a sulfur atom, and B represents the following formula: [ka] It is one of the following. Item 9. The photosensitive resin composition according to item 8, wherein the photosensitive resin composition is represented by the formula:

[10] The Y1 is represented by the following formula: [ka] or the following formula: [ka] or the following formula: [ka] Item 10. The photosensitive resin composition according to item 9, wherein the structure is represented by:

[11] The X1 is represented by the following formula (X1): [ka] In the formula, each Ry independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, C represents an oxygen atom or a sulfur atom, and D represents a group represented by the following formula: [ka] It is one of the following. The photosensitive resin composition according to any one of items 8 to 10, wherein the photosensitive resin composition is represented by the following formula:

[12] The X1 is represented by the following formula: [ka] or the following formula: [ka] Item 12. The photosensitive resin composition according to item 11, wherein the structure is represented by:

[13] 13. The photosensitive resin composition according to any one of items 1 to 12, wherein the (B) photosensitizer is a photoradical polymerization initiator.

[14] 14. The photosensitive resin composition according to any one of items 1 to 13, which is a negative photosensitive resin composition.

[15] A method for producing a cured film obtained from a photosensitive resin composition comprising 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, the cured film being represented by the following formula (i): 0.001<(tan δ 40 -tan δ 10 ) / tan δ 10 <0.2 (i) {where, tanδ 40 indicates the dielectric tangent at a frequency of 40 GHz using the perturbation split cylinder resonator method, and tanδ 10 A method for producing a cured film that satisfies the following criteria: {R is the dielectric tangent at a frequency of 10 GHz, as determined by the perturbation split cylinder resonator method}.

[16] A method for producing a cured film obtained from a photosensitive resin composition comprising 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, the cured film being represented by the following formula (ii): 0.001<(tan δ 60 -tan δ 10 ) / tan δ 10 <0.29 (ii) {where, tanδ 60 indicates the dielectric tangent at a frequency of 60 GHz using the perturbation split cylinder resonator method, and tanδ 10 A method for producing a cured film that satisfies the following criteria: {R is the dielectric tangent at a frequency of 10 GHz, as determined by the perturbation split cylinder resonator method}.

[17] A method for producing a cured film obtained from a photosensitive resin composition comprising 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, the cured film being represented by the following formulas (i) and (ii): 0.001<(tan δ 40 -tan δ 10 ) / tan δ 10 <0.2 (i) 0.001<(tan δ 60 -tan δ 10 ) / tan δ 10 <0.29 (ii) {where, tanδ 40 indicates the dielectric tangent at a frequency of 40 GHz using the perturbation split cylinder resonator method, and tanδ 10 indicates the dielectric tangent at a frequency of 10 GHz using the perturbation split cylinder resonator method, and tanδ 60 A method for producing a cured film that satisfies the following criteria: {R2 is a dielectric tangent at a frequency of 60 GHz, as determined by a perturbation split cylinder resonator method}.

[18] 18. The method for producing a cured film according to any one of items 15 to 17, wherein the photosensitizer contained in the photosensitive resin composition is a photoradical polymerization initiator.

[19] 19. The method for producing a cured film according to any one of items 15 to 18, wherein the photosensitive resin composition is a negative photosensitive resin composition.

[20] 20. The method for producing a cured film according to any one of items 15 to 19, wherein the photosensitive resin composition contains an agent for reducing dielectric tangent. Effect of the Invention

[0009] According to the present invention, it is possible to provide a photosensitive resin composition having good storage stability and a low dielectric loss tangent while maintaining the resolution of the relief pattern formed. In one embodiment, the dielectric loss tangent can be reduced by reducing the polarity of the cured film. In one embodiment, the resins are mixed with good compatibility with each other, so that the composition can be stored without phase separation, and the resolution when the relief pattern is formed can be maintained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the form for carrying out the present invention (hereinafter, abbreviated as "embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and can be carried out in various modifications within the scope of the gist. Throughout this specification, when a structure represented by the same symbol in a general formula is present in a molecule, it is independently selected and may be the same as or different from each other, unless otherwise specified. Furthermore, structures represented by a common symbol in different general formulas are also independently selected and may be the same as or different from each other, unless otherwise specified.

[0011] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment includes (A) a polyimide precursor, (B) a photosensitizer, (C) a dielectric loss tangent reducing agent, and (D) a solvent. If desired, the photosensitive resin composition includes other components. Each component will be described in turn below.

[0012] The photosensitive resin composition may be either a negative type or a positive type depending on the desired application, and is preferably a negative type from the viewpoint of the physical properties of the (A) polyimide precursor described below.

[0013] (A) Polyimide precursor In this embodiment, the polyimide precursor (A) is a resin component contained in the photosensitive resin composition, and is represented by the following general formula (1): [ka] In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is represented by the following general formula (2): [ka] (In formula (2), R3, R4, and R5 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.) It is a group represented by the following formula: It is preferable that the polyamide has a structural unit represented by the following formula (1):

[0014] The ratio of the monovalent organic group represented by the above general formula (2) to all of R1 and R2 of the precursor represented by the above general formula (1) contained in the (A) polyimide precursor is preferably 50 mol % to 100 mol % from the viewpoint of high resolution, and more preferably 75 mol % to 100 mol % from the viewpoints of high chemical resistance and sensitivity.

[0015] In the above general formula (1), n1 is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0016] In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group and the -COOR2 group are at the ortho position relative to the -CONH- group, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as the following general formula (20): [ka] {In formula (20), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} Examples of the X1 structure include, but are not limited to, a group having a structure represented by the following formula (20): In addition, the X1 structure may be one type or a combination of two or more types. The X1 group having the structure represented by the following formula (20) is particularly preferred in that it has both heat resistance and photosensitive properties.

[0017] In addition, in the above general formula (1), the tetravalent organic group represented by X1 is preferably represented by the following formula (X1): [ka] In the formula, each Ry independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, C represents an oxygen atom or a sulfur atom, and D represents a group represented by the following formula: [ka] It is one of the following. It is preferably represented by the following formula: [ka] or the following formula: [ka] It is more preferable that the structure is represented by the following formula:

[0018] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (21): [ka] {In formula (21), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} Examples of the structure represented by the formula (21) include, but are not limited to, the structure represented by the formula (21) above. The structure represented by the formula (21) above is particularly preferred in that it provides both heat resistance and photosensitive properties.

[0019] As the Y1 group, among the structures represented by the above formula (21), the following formula is particularly preferred: [ka] The structure represented by the following formula is preferable from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance. [ka] The structure represented by the formula (1) is preferable from the viewpoint of low dielectric tangent.

[0020] In addition, in the above general formula (1), the divalent organic group represented by Y1 is preferably represented by the following formula (Y1): [ka] In the formula, Rz each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, A represents an oxygen atom or a sulfur atom, and B represents the following formula: [ka] It is one of the following. It is preferably represented by the following formula: [ka] or the following formula: [ka] or the following formula: [ka] It is more preferable that the structure is represented by the following formula:

[0021] In the above general formula (2), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitive properties. Also, m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

[0022] (A) Method for preparing polyimide precursor The polyimide precursor including the structure represented by the general formula (1) in the present embodiment can be obtained, for example, by a method including reacting a tetracarboxylic dianhydride including the tetravalent organic group X1 having 6 to 40 carbon atoms with (a) an alcohol having a structure in which a monovalent organic group represented by the general formula (2) and a hydroxyl group are bonded, and, if desired, with (b) an alcohol having a structure other than the group represented by the general formula (2) to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester body); and subsequently polycondensing the obtained acid / ester body with a diamine including the divalent organic group Y1 having 6 to 40 carbon atoms.

[0023] (Preparation of Acid / Ester Forms) In this embodiment, examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 having 6 to 40 carbon atoms include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. These may be used alone or in combination of two or more.

[0024] (b) Examples of alcohols having a structure other than the group represented by general formula (2) above include aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, such as 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0025] The content of the organic group of general formula (2) in the polyimide precursor is preferably 50 mol % or more relative to the total content of R1, R2, R6, and R7. When the content of the organic group of general formula (2) exceeds 50 mol %, it is preferable because the desired photosensitive characteristics can be obtained. The content of the organic group of general formula (2) in the photosensitive resin composition is preferably 75 mol % or more based on the total content of R1, R2, R6, and R7.

[0026] The above tetracarboxylic dianhydride and the above (a) alcohol are dissolved and mixed in a reaction solvent in the presence of a basic catalyst such as pyridine, whereby a half-esterification reaction of the acid dianhydride proceeds to obtain the desired acid / ester. The reaction conditions are preferably a reaction temperature of 20 to 50°C and stirring for 4 to 10 hours.

[0027] The reaction solvent is preferably one that dissolves the acid / ester and the polyimide precursor, which is a polycondensation product of the acid / ester and diamine. Examples of the reaction solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination as needed.

[0028] (Preparation of polyimide precursor) A known dehydration condensation agent is mixed with the above acid / ester (typically a solution in the above reaction solvent) under ice cooling to convert the acid / ester into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 having 6 to 40 carbon atoms dissolved or dispersed in a separate solvent is added dropwise to the acid / ester to polycondense, thereby obtaining a polyimide precursor. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

[0029] Examples of diamines containing a divalent organic group Y1 having 6 to 40 carbon atoms include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4 '-Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl] 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]ether, bis(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidinesulfone, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl}propane, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,Also included are 2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamines are not limited to these.

[0030] In order to improve adhesion between the photosensitive resin layer formed on a substrate by applying the photosensitive resin composition of the present embodiment onto the substrate and various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized during preparation of the polyimide precursor (A).

[0031] After the polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution may be filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof may be added to the reaction solution to precipitate the polymer component. Furthermore, the polymer may be purified by repeating the above-mentioned redissolution and reprecipitation operations. The polymer may then be vacuum-dried to isolate the polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0032] The molecular weight of the polyimide precursor (A), as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000. When the weight average molecular weight is 8,000 or more, it is preferable because the mechanical properties are good, while when it is 150,000 or less, it is preferable because the dispersibility in the developer and the resolution performance of the relief pattern are good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0033] (B) Photosensitizer The photosensitive resin composition of the present embodiment contains a photosensitizer. In one embodiment, the photosensitizer may be a photopolymerization initiator. The photopolymerization initiator is preferable because it promotes the curing of the relief pattern by light irradiation. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples of the photopolymerization initiator include benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxy)-2 ... Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0034] The amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass of the polyimide precursor (A). The amount is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and is preferably 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0035] (C) Low dielectric tangent agent The photosensitive resin composition of the present embodiment contains a dielectric loss tangent reducing agent. The dielectric loss tangent reducing agent (C) is a compound that, when used as an additive in a resin composition, gives a cured film obtained from a composition of the dielectric loss tangent reducing agent (C) and a resin, a dielectric loss tangent at 40 GHz that is 5 to 80% lower than the dielectric loss tangent of a resin composition that does not contain the dielectric loss tangent reducing agent (C).

[0036] The molecular weight of the dielectric loss tangent reducing agent is preferably 5,000 or less, more preferably 3,500 or less, from the viewpoint of solubility, and is preferably 100 or more, from the viewpoint of reducing the dielectric loss tangent.

[0037] (C) The structure of the low dielectric loss tangent agent is not limited as long as it reduces the dielectric loss tangent, but from the viewpoint of the thermal properties of the cured film, a substituted benzene structure is preferred. The substituent structure in the substituted benzene structure is not limited, but examples thereof include alkyl groups, ester groups, ether groups, phenyl groups, hydroxy groups, ketone groups, carboxy groups, peroxide groups, amino groups, imino groups, imide groups, amide groups, isocyanate groups, sulfo groups, epoxy groups, fluoro groups, nitro groups, thiol groups, phosphonyl groups, and isocyanuric groups, and from the viewpoint of low dielectric loss tangent, preferred are alkyl groups, ester groups, ether groups, amide groups, phenyl groups, and phosphonyl groups. Among these, from the viewpoint of low dielectric loss tangent, it is more preferred to have an alkyl group.

[0038] (C) The dielectric loss tangent reducing agent may have one, two or more, or three or more benzene structures in the same molecule. When the dielectric loss tangent reducing agent has one benzene structure, the compound represented by the following formula (I) may be used. [ka] {In the formula, R1, R4, and R5 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2 and R3 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms; and Z is an organic group having 7 to 80 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or an organic group having 2 to 15 carbon atoms and containing a carbonyl group.} A compound having a structure represented by the following formula is preferred.

[0039] In the case where there is one benzene structure, the (C) dielectric loss tangent reducing agent preferably has an organic group having 2 to 15 carbon atoms containing a carbonyl group and a benzene ring which may have a substituent, from the viewpoints of storage stability, relief pattern resolution, low dielectric tangent, low polarity, compatibility with resins, and the like, and is represented by the following formula: [ka] {In the formula, Z is an organic group containing a carbonyl group and having 2 to 15 carbon atoms.} It is more preferable that the compound has a structure represented by at least one of the following:

[0040] More specifically, examples of the (C) low dielectric tangent agent having one benzene structure include, but are not limited to, the following compound groups: [ka]

[0041] (C) In the case where the dielectric loss tangent reducing agent has two benzene structures in the same molecule, the compound represented by the following formula (II): [ka] {wherein R1, R4, R5, R6, R7, and R 10are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2, R3, R8, and R9 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms; and Z is a divalent organic group having 1 to 50 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a divalent organic group having 1 to 75 carbon atoms.} The structure represented by the following formula is preferred.

[0042] More specifically, examples of the (C) low dielectric tangent agent having two benzene structures include, but are not limited to, the following compound groups: [ka] [ka] [ka] [ka] [ka] [ka]

[0043] (C) When the dielectric loss tangent reducing agent has three benzene structures in the same molecule, the compound represented by the following formula (III): [ka] {wherein R1, R4, R5, R6, R9, and R 10 and R 11 and R 12 and R 15 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2, R3, R8, R7, and R 13 and R 14are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms, and Z is a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.} It is preferable that the compound has a structure represented by the following formula:

[0044] More specifically, examples of the (C) low dielectric tangent agent having three benzene structures include, but are not limited to, the following compound groups: [ka] [ka] [ka] [ka]

[0045] (C) When the dielectric loss tangent reducing agent has four or more benzene structures in one molecule, the dielectric loss tangent reducing agent has the following general formula (IV): [ka] {wherein R1, R4, R5, R6, R7, and R 10 and R 11 and R 12 and R 15 and R 16 and R 19 and R 20 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R2, R3, R8, R9, and R 13 and R 14 and R 17 and R 18are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 50 carbon atoms, and Z is a tetravalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from sulfur, phosphorus, oxygen, and nitrogen, or a tetravalent organic group having 1 to 50 carbon atoms.) or a compound represented by the following general formula (V): [ka] {wherein R1 and R2 and R4 and R5 and R6 and R7 and R9 and R 10 and R 11 and R 12 and R 14 and R 15 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R, R, and R 13 are each independently a hydrogen atom or an organic group having 1 to 10 carbon atoms, X is an organic group having 1 to 5 carbon atoms which may contain an oxygen atom, and Z is a hydrogen atom, a trivalent organic group containing at least one heteroatom selected from sulfur, phosphorus, oxygen and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.}, or a group represented by the following general formula (VI): [ka] {wherein R1, R3, R4, R5, R6, R8, R9, and R 10 and R 11 and R 12 and R 13 and R 15 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R and R and R 14 are each independently a hydrogen atom or an organic group having 1 to 10 carbon atoms, X is an organic group having 1 to 5 carbon atoms which may contain an oxygen atom, and Z is a hydrogen atom, a trivalent organic group containing at least one heteroatom selected from sulfur, phosphorus, oxygen and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.}, or a group represented by the following general formula (VII): [ka] {wherein R1 and R2 and R4 and R5 and R6 and R7 and R9 and R10 are each independently a hydrogen atom, a methyl group, or a t-butyl group; R3 and R8 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms; R4, R7, and R 12 are each independently a hydrogen atom or an organic group having 1 to 10 carbon atoms, X is an organic group having 1 to 5 carbon atoms which may contain an oxygen atom, and Z is a hydrogen atom, a divalent organic group containing at least one heteroatom selected from sulfur, phosphorus, oxygen and nitrogen, or a divalent organic group having 1 to 50 carbon atoms.

[0046] (C) When the dielectric loss tangent reducing agent has four or more benzene structures in one molecule, examples of the compound include, but are not limited to, the following compounds: [ka] [ka] [ka]

[0047] The (C) dielectric loss tangent reducing agent is not limited in synthesis method, but can be obtained as a reaction product of a phenol compound and an acid chloride compound, for example. Preferably, a solution is obtained by mixing a phenol compound with a basic catalyst and a solvent, and an acid chloride compound is added to the solution and reacted to produce the (C) dielectric loss tangent reducing agent. The reaction is not particularly limited as long as the peak derived from the reaction residue disappears in liquid chromatography, but for example, the reaction temperature may be heated to 30°C after adding the acid chloride at -10°C to 0°C, or may be kept constant at -10°C to 0°C. After synthesis, the basic catalyst is removed by passing through a column filled with a cation exchange resin, and the mixture is diluted with a solvent and separated and purified with a basic solution and water, and the solvent is distilled off with an evaporator to obtain the (C) dielectric loss tangent reducing agent. The cation exchange resin is not particularly limited, but it is preferable to use a weakly acidic ion exchange resin. Examples of the solvent used for the separation include, but are not limited to, toluene, ethyl acetate, diethyl ether, dichloromethane, benzene, and hexane.

[0048] (C) Phenol compounds used in the synthesis reaction of the low dielectric tangent agent include, but are not limited to, structures represented by the following general formula: [ka]

[0049] (C) The acid chloride compound used in the synthesis reaction of the dielectric dissipation factor enhancer includes, but is not limited to, structures represented by the following general formula: [ka]

[0050] The blending amount of the low dielectric tangent agent is preferably 0.1 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 60 parts by mass or less, more preferably 2 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 32 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 parts by mass or more from the viewpoint of low dielectric tangent of the cured film, and 32 parts by mass or less from the viewpoint of photosensitivity or patterning property.

[0051] The photosensitive resin composition of the present embodiment contains the above-mentioned low dielectric tangent agent, and thus can provide a resin film having a low dielectric tangent in the high frequency range (10 to 80 GHz) and low frequency dependency while maintaining resolution and storage stability. Although not bound by theory, the reason for the decrease in dielectric tangent is believed to be that the dipole moment of the (C) low dielectric tangent agent itself is small, which reduces the ratio of polar functional groups such as imide groups and amide groups in the entire film. Although not bound by theory, the reason for the low frequency dependency is believed to be that the polarity of the entire film is reduced, which reduces the water absorption rate during film formation. Although not bound by theory, the reason for maintaining resolution and storage stability is believed to be that the molecular weight is 100 to 3,500, and polyimide precursors with different polarities are mixed in the resin composition and in the cured film without phase separation.

[0052] (D) Solvent The photosensitive resin composition of the present embodiment contains a solvent. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) polyimide precursor. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and 2-octanone, which can be used alone or in combination of two or more.

[0053] The above-mentioned solvent can be used in an amount of, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass, and more preferably 100 parts by mass to 860 parts by mass, relative to 100 parts by mass of the polyimide precursor (A), depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0054] From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferred. The alcohols that can be suitably used are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond, and specific examples thereof include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol; lactate esters such as ethyl lactate; propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, and propylene glycol-2-(n-propyl) ether; monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether; 2-hydroxyisobutyric acid esters; and dialcohols such as ethylene glycol and propylene glycol. Of these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, and in particular, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are more preferred.

[0055] When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, based on the mass of the total solvent. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good, while when it is 50% by mass or less, the solubility of the (A) polyimide precursor becomes good, which is preferable.

[0056] In one embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, and 1,6-hexaacrylate. Examples of suitable compounds include diacrylate and dimethacrylate of Sandiol, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0057] The amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass based on 100 parts by mass of the (A) polyimide precursor.

[0058] In one embodiment, the photosensitive resin composition may optionally contain an adhesion promoter in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthala. Examples of the adhesive agent include silane coupling agents such as amido acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0059] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The amount of the adhesion aid to be added is preferably within a range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0060] In one embodiment, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, 4-methoxyphenol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0061] The amount of the thermal polymerization inhibitor to be added is preferably within a range of 0.005 parts by mass to 12 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0062] For example, when a substrate made of copper or a copper alloy is used, the photosensitive resin composition may optionally contain an azole compound in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0063] The amount of the azole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while when the amount is 20 parts by mass or less, photosensitivity is excellent, which is preferable.

[0064] In this embodiment, in order to suppress discoloration on copper, the photosensitive resin composition may contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butyl phenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylfuran phenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2, 4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)- 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine Examples of the triazine-2,4,6-(1H,3H,5H)-trione include 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0065] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, photosensitivity is excellent, which is preferable.

[0066] In one embodiment, the photosensitive resin composition may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250°C.

[0067] Examples of organotitanium compounds that can be used include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.

[0068] Specific examples of the organotitanium compound are shown below in I) to VII): I) As the titanium chelate compound, a titanium chelate having two or more alkoxy groups is more preferable because it provides the storage stability of the photosensitive resin composition and a good pattern. Specific examples of the titanium chelate compound include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0069] II) Examples of tetraalkoxytitanium compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}].

[0070] III) Titanocene compounds include, for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0071] IV) Examples of monoalkoxytitanium compounds include titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.

[0072] V) Examples of titanium oxide compounds include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), and phthalocyanine titanium oxide.

[0073] VI) Titanium tetraacetylacetonate compounds include, for example, titanium tetraacetylacetonate.

[0074] VII) Titanate coupling agents include, for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0075] Among the above I) to VII), it is preferable that the organic titanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0076] When an organic titanium compound is blended, the blending amount is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 2 parts by mass, relative to 100 parts by mass of the (A) resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the blending amount is 10 parts by mass or less, excellent storage stability is obtained, which is preferable.

[0077] [Polyimide] The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is preferably represented by the following general formula (11). [ka] {In general formula (11), X 1 and Y 1 are the same as X1 and Y1 in general formula (1), and m is a positive integer. For the same reason, the preferred X1 and Y1 in the general formula (1) are also preferred in the polyimide of the general formula (11). The number m of repeating units in the general formula (11) is not particularly limited, but may be an integer of 2 to 150. According to the present invention, there can also be provided a method for producing a polyimide, which includes a step of converting the above-described photosensitive resin composition into a polyimide.

[0078] [Cured film and its manufacturing method] In another embodiment of the present invention, there is provided a cured film obtained from the above-described photosensitive resin composition and a method for producing the same, wherein the cured film has a structure represented by the following formula (i) and / or (ii): 0.001<(tan δ 40 -tan δ 10 ) / tan δ 10 <0.2 (i) {where, tanδ 40 indicates the dielectric tangent at a frequency of 40 GHz using the perturbation split cylinder resonator method, and tanδ 10 indicates the dielectric tangent at a frequency of 10 GHz using the perturbation split cylinder resonator method. 0.001<(tan δ 60 -tan δ 10 ) / tan δ 10 <0.29 (ii) {where, tanδ 60 indicates the dielectric tangent at a frequency of 60 GHz using the perturbation split cylinder resonator method, and tanδ 10 indicates the dielectric tangent at a frequency of 10 GHz using the perturbation split cylinder resonator method. The relationship expressed as:

[0079] When the above formula (1) and / or (ii) is satisfied, the polarity of the cured film can be reduced, thereby reducing the dielectric loss tangent, and by mixing the resins with good compatibility, the resins can be stored without phase separation, and the resolution during the formation of a relief pattern tends to be maintained. 0.002<(tan δ 40 -tan δ 10 ) / tan δ 10 <0.1909; and / or 0.002<(tan δ 60 -tan δ 10 ) / tan δ 10 <0.2789 It is preferable that the dielectric loss tangent satisfies the following: The dielectric loss tangent can be measured by a perturbation type split cylinder resonator method shown in the examples described later.

[0080] From the viewpoint of satisfying the above mathematical formula (1) and / or (ii), the photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, more preferably contains a photoradical polymerization initiator as a photosensitizer and / or contains a low dielectric tangent agent, and further preferably the photosensitive resin composition is a negative type.

[0081] Specific steps in the method for producing a cured film can be performed in accordance with steps (1) to (4) of the method for producing a cured relief pattern described below.

[0082] [Hardened relief pattern] According to the present invention, it is possible to provide a cured relief pattern using the photosensitive resin composition described above, and a method for producing the same. In one embodiment, the method for producing a cured relief pattern includes the following steps (1) to (4): (1) applying the photosensitive resin composition according to the present embodiment onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat treating the relief pattern to form a hardened relief pattern; The method includes:

[0083] Each step will be described below. (1) A step of applying the photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate. In this step, the photosensitive resin composition according to this embodiment is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, or a method of spray application using a spray coater, can be used.

[0084] If necessary, the coating film made of the photosensitive resin composition can be dried, and examples of the drying method include air drying, heat drying using an oven or a hot plate, and vacuum drying. It is preferable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor in the photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

[0085] (2) A step of exposing the photosensitive resin layer to light In this process, the photosensitive resin layer formed in the above process (1) is exposed to an ultraviolet light source or the like through a patterned photomask or reticle or directly using an exposure device such as a contact aligner, mirror projection, or stepper.

[0086] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any combination of temperature and time as necessary for the purpose of improving photosensitivity, etc. The range of baking conditions is preferably a temperature of 40° C. to 120° C. and a time of 10 seconds to 240 seconds, but is not limited to this range as long as it does not impair the various properties of the negative photosensitive resin composition.

[0087] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern. In this step, when the photosensitive resin composition is a negative type, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. In addition, after development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at any combination of temperature and time as necessary. As the developer used for development, for example, a good solvent for the negative type photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferable. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more kinds of each solvent, for example, several kinds, can be used in combination.

[0088] (4) heat treating the relief pattern to form a hardened relief pattern; In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component and imidize the polyimide precursor (A), thereby converting it into a cured relief pattern made of polyimide. As a method for heat curing, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-elevating oven that can set a temperature program. Heating can be performed, for example, under conditions of 150°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may also be used.

[0089] [Semiconductor Devices] The photosensitive resin composition of the present embodiment can also provide a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern. Thus, a semiconductor device can be provided having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for producing a cured relief pattern. The present invention can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of the process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

[0090] [Display device] The photosensitive resin composition of the present embodiment can also provide a display device comprising a display element and a cured film provided on the upper portion of the display element, the cured film being the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. For example, the cured film can be a surface protective film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for a cathode of an organic EL element.

[0091] The photosensitive resin composition of the present invention is useful not only for application to the above-mentioned semiconductor devices, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. EXAMPLES

[0092] The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

[0093] [Measurement and evaluation methods] (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene equivalent). The column used in the measurement was "Shodex 805M / 806M in series" manufactured by Showa Denko K.K., the standard monodisperse polystyrene was "Shodex STANDARD SM-105" manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K.

[0094] (2) Esterification rate The progress of the reaction between the phenolic compound and the acid chloride was measured by gel permeation chromatography. The column used for the measurement was "Shodex 802 / 801 / 801 in series" manufactured by Showa Denko K.K. The developing solvent was tetrahydrofuran, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K. The reaction was considered to be complete when the integral ratio of the peak derived from the acid chloride became 1% or less of the total peak integral ratio.

[0095] (3) Resolution of hardened relief patterns on Cu A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with 200 nm of Ti and 400 nm of Cu, in that order, using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Next, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.), and dried to form a coating film with a thickness of 10 μm. Using a test pattern mask, this coating film was then sprayed with 250 mJ / cm using Prisma GHI (manufactured by Ultratech Co., Ltd.) equipped with an i-line filter. 2The coating was then spray-developed with a coater developer (D-Spin60A, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer with the relief pattern formed on Cu was heat-treated in a temperature-programmed curing furnace (VF-2000 model, manufactured by Koyo Lindberg) under a nitrogen atmosphere at 230°C for 2 hours to obtain a cured relief pattern made of resin approximately 6 to 7 μm thick on Cu. The relief pattern thus produced was observed under an optical microscope to determine the size of the minimum opening pattern. If the area of ​​the opening of the obtained pattern was at least half the area of ​​the corresponding pattern mask opening, it was deemed to be resolved, and the length of the mask opening side corresponding to the opening with the smallest area among the resolved openings was taken as the resolution. "Excellent": The minimum opening pattern size is less than 10 μm "Good": The minimum opening pattern size is 10 μm or more and less than 14 μm "Acceptable": The minimum opening pattern size is 14 μm or more and less than 18 μm "Not acceptable": The minimum opening pattern size is 18 μm or more.

[0096] (4) Storage stability evaluation After preparing the photosensitive resin composition, it was stirred for 3 days at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) and then its condition was evaluated. The evaluation results were rated as "good" when the entire composition was mixed, and "poor" when phase separation occurred in the resin composition.

[0097] (5) Dielectric constant and dielectric loss tangent measurement A 100 nm thick aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The negative photosensitive resin composition was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin60A model, manufactured by SOKUDO Co., Ltd.), and then heated and dried at 110°C for 180 seconds to produce a spin-coated film. Then, an aligner (PLA-501F, manufactured by Canon Co., Ltd.) was used to expose the film to an exposure dose of 600 mJ / cm. 2 The entire surface was exposed to ghi rays, and a heat curing treatment was performed for 2 hours at 230°C in a nitrogen atmosphere using a vertical curing furnace (Koyo Lindberg, model name VF-2000B) to produce a cured film. The thickness of the cured film was measured using the method described below. This cured film was cut into a length of 80 mm and a width of 60 mm or a length of 40 mm and a width of 30 mm using a dicing saw (Disco, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid solution, and peeled off from the silicon wafer to prepare a film sample.

[0098] The relative dielectric constant and dielectric loss tangent of the film sample were calculated at 10, 28, 40, and 60 GHz using the resonator perturbation method. The details of the measurement method are as follows. (Measurement method) Perturbation split cylinder resonator method (Device configuration) Network analyzer: PNA Network analyzer E5224B (Agilent Technologies) Split cylinder resonators: CR-710 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 10 GHz), CR-728 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 28 GHz), CR-740 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 40 GHz), CR-760 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 60 GHz)

[0099] (6) Film thickness measurement A 100 nm thick aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The negative photosensitive resin composition was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin60A model, manufactured by SOKUDO Co., Ltd.), and then heated and dried at 110°C for 180 seconds to produce a spin-coated film. Then, an aligner (PLA-501F, manufactured by Canon Co., Ltd.) was used to expose the film to an exposure dose of 600 mJ / cm. 2 The entire surface was exposed to ghi rays, and then a heat curing treatment was performed for 2 hours at 230°C in a nitrogen atmosphere using a vertical curing furnace (Koyo Lindberg, model name VF-2000B) to produce a cured film. The film thickness of the cured film was measured using a step gauge (P-15, KLA-Tenchore).

[0100] <Production Example 1> (A) Synthesis of polyimide precursor (polymer A-1) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generation by the reaction had ceased, the mixture was allowed to cool to room temperature and then left to stand for another 16 hours.

[0101] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by a suspension of 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 ml of γ-butyrolactone over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, after which 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0102] The reaction solution thus obtained was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution thus obtained was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM15") to obtain a polymer solution. The obtained polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and dried in vacuum to obtain a powdered polymer A-1. The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 22,000.

[0103] <Production Example 2> (Synthesis of polyimide precursor (polymer A-2)) Polymer A-2 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that 175.9 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (BAPP) was used instead of 93.0 g of ODA in Production Example 1. The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 24,000.

[0104] <Production Example 3> (Synthesis of polyimide precursor (polymer A-3)) Polymer A-3 was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 169.9 g of bis{4-(4-aminophenoxy)phenyl}ketone was used instead of 93.0 g of ODA in Production Example 1. The weight average molecular weight (Mw) of this polymer A-3 was measured and found to be 21,000.

[0105] <Production Example 4> (Synthesis of polyimide precursor (polymer A-4)) Polymer A-4 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA in Production Example 1. The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 29,000.

[0106] <Production Example 5> (Synthesis of polyimide precursor (polymer A-5)) Polymer A-5 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that in Production Example 2, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used instead of 155.1 g of ODPA, and 169.9 g of bis{4-(4-aminophenoxy)phenyl}ketone was used instead of 93.0 g of ODA. The weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 28,000.

[0107] <Production Example 6> (Synthesis of polyimide precursor (polymer A-6)) Polymer A-6 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that 77.6 g of ODPA and 130.1 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride were used instead of 155.1 g of ODPA, and 175.9 g of BAPP were used instead of 93.0 g of ODA in Production Example 1. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 24,000.

[0108] <Production Example 7> (Synthesis of polyimide precursor (polymer A-7)) Polymer A-7 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that 73.6 g of BPDA and 130.1 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride were used instead of 155.1 g of ODPA, and 175.9 g of BAPP were used instead of 93.0 g of ODA in Production Example 1. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 24,000.

[0109] <Production Example 8> (Synthesis of polyimide precursor (polymer A-8)) Polymer A-8 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that 219.3 g of 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl}propane (MBAPP) was used instead of 93.0 g of ODA in Production Example 1. The weight average molecular weight (Mw) of this polymer A-8 was measured and found to be 25,000.

[0110] <Production Example 9> (Synthesis of low dielectric tangent agent C-1) 38.3 g of Adeka STAB AO-40 (ADEKA) was placed in a 1 L separator flask under a nitrogen atmosphere, and 383 g of toluene and 60.7 g of triethylamine (TEA) were added and dissolved at room temperature. Next, 29.6 g of 3,3-dimethylbutyryl chloride was added under ice cooling, and after it was confirmed that the temperature did not rise any more, the mixture was heated to 30°C and reacted for 1 hour. After confirming the completion of the reaction by GPC, the resulting reaction solution was immersed in an anion exchange resin (Organo Corporation's "Amberlyst" TM 15") was added to the purified reaction solution, which was then transferred to a separatory funnel and purified three times with a saturated aqueous solution of sodium bicarbonate and ten times with water. The solvent was removed from the resulting organic layer using an evaporator, yielding low dielectric tangent agent C-1, which is mainly composed of the following compound. [ka]

[0111] <Production Example 10> (Synthesis of low dielectric tangent agent C-2) A reaction was carried out in the same manner as in Production Example 9, except that 74.1 g of AO-80 (manufactured by ADEKA) was used instead of 38.3 g of Adeka STAB AO-40 (ADEKA), to obtain a low dielectric tangent agent C-2 containing the following compound as a main component. [ka]

[0112] <Production Example 11> (Synthesis of low dielectric tangent agent C-3) 54.5 g of Adeka STAB AO-30 (ADEKA) was placed in a 1 L separator flask under a nitrogen atmosphere, and 545 g of toluene and 91.1 g of triethylamine (TEA) were added and dissolved at room temperature. Next, 44.4 g of 3,3-dimethylbutyryl chloride was added under ice cooling, and after it was confirmed that the temperature did not rise any more, the mixture was heated to 30°C and reacted for 1 hour. After confirming the completion of the reaction by GPC, the resulting reaction solution was immersed in an anion exchange resin (Organo Corporation's "Amberlyst" TM 15") was added to the purified reaction solution, which was then transferred to a separatory funnel and purified three times with a saturated aqueous solution of sodium bicarbonate and ten times with water. The solvent was removed from the organic layer using an evaporator, yielding low dielectric tangent agent C-3, which is mainly composed of the following compound. [ka]

[0113] <Production Example 12> (Synthesis of low dielectric tangent agent C-4) A reaction was carried out in the same manner as in Production Example 11, except that 69.9 g of cyanox1790 was used instead of 54.5 g of Adeka STAB AO-30 (manufactured by ADEKA), to obtain a low dielectric tangent agent C-4 containing the following compound as a main component. [ka]

[0114] <Production Example 13> (Synthesis of low dielectric tangent agent C-5) A low dielectric tangent agent C-5 containing the following compound as a main component was obtained by carrying out a reaction in the same manner as in Production Example 11, except that 69.9 g of cyanox1790 was used instead of 54.5 g of Adeka STAB AO-30 (manufactured by ADEKA) and 49.0 g of heptanoyl chloride was used instead of 44.4 g of 3,3-dimethylbutyryl chloride. [ka]

[0115] <Production Example 14> (Synthesis of low dielectric tangent agent C-6) A reaction was carried out in the same manner as in Production Example 11, except that 69.9 g of cyanox1790 was used instead of 54.5 g of Adeka STAB AO-30 (manufactured by ADEKA), and 34.5 g of methacryloyl chloride was used instead of 44.4 g of 3,3-dimethylbutyryl chloride, to obtain a low dielectric tangent agent C-6 containing the following compound as a main component. [ka]

[0116] <Production Example 15> (Synthesis of low dielectric tangent agent C-7) A reaction was carried out in the same manner as in Production Example 11, except that 69.9 g of cyanox1790 was used instead of 54.5 g of Adeka STAB AO-30 (manufactured by ADEKA), and 46.4 g of benzoyl chloride was used instead of 44.4 g of 3,3-dimethylbutyryl chloride, to obtain a low dielectric tangent agent C-7 containing the following compound as a main component. [ka]

[0117] <Production Example 16> (Synthesis of low dielectric tangent agent C-8) 63.3 g of 4,4',4'',4'''-[(1-methylethylidene)-1-ylidene]tetrakis[2-methylphenol] (Honshu Chemical Industry Co., Ltd.) was placed in a 1 L separator flask under a nitrogen atmosphere, and 63.3 g of toluene and 121.4 g of triethylamine (TEA) were added and dissolved at room temperature. Next, 44.4 g of 3,3-dimethylbutyryl chloride was added under ice cooling, and after it was confirmed that the temperature no longer increased, the mixture was heated to 30°C and reacted for 1 hour. After confirming the completion of the reaction by GPC, the resulting reaction solution was immersed in an anion exchange resin (Amberlyst, Organo Corporation). TM15") was added to the purified reaction solution, which was then transferred to a separatory funnel after adding 300 mL of ethyl acetate. The solution was then purified by separation three times with a saturated aqueous solution of sodium bicarbonate and ten times with water. The solvent was removed from the organic layer using an evaporator, and low dielectric tangent agent C-8, which is mainly composed of the following compound, was obtained. [ka]

[0118] (C) As the dielectric loss tangent reducing agent, the following compounds were used as provided. C-9: SR-3000 (manufactured by Daihachi Chemical) C-10: PX-200 (manufactured by Daihachi Chemical)

[0119] The following compounds were used in the examples and comparative examples. Photopolymerization initiator B-1: PBG-304 (manufactured by Changzhou Strong Electronics Co., Ltd.) Photopolymerization initiator B-2: PBG-305 (manufactured by Changzhou Strong Electronics Co., Ltd.) Photopolymerization initiator B-3: PBG-3057 (manufactured by Changzhou Strong Electronics Co., Ltd.) Solvent D-1: γ-butyrolactone Solvent D-2: Dimethyl sulfoxide (DMSO) Solvent D-3: N-methyl-2-pyrrolidone Polymer E-1: Polystyrene (weight average molecular weight: 20,000)

[0120] <Example 1> 100 g of polymer A-1 as component (A), 5 g of photopolymerization initiator B-1 as component (B), and 15 g of low dielectric tangent agent C-1 as component (C) were dissolved in γ-butyrolactone (200 g) to prepare a photosensitive resin composition solution. This composition was evaluated by the methods described above, and the evaluation results are shown in Table 1.

[0121] <Examples 2 to 24 and Comparative Examples 1 to 3> The evaluation was carried out in the same manner as in Example 1, except that the resin composition solutions were prepared in the proportions shown in Tables 1 and 2. The evaluation results are shown in Tables 1 and 2.

[0122] [Table 1-1]

[0123] [Table 1-2]

[0124] [Table 2-1]

[0125] [Table 2-2]

[0126] As is clear from Tables 1 and 2, the dielectric tangents of the Examples were lower than those of Comparative Example 1, regardless of the measurement frequency. In Comparative Example 2, the polyimide resin and polystyrene were phase-separated, and the pattern after development had an opening of 40 μm or more. In Comparative Example 3, the (C) low dielectric tangent agent was phase-separated from the polyimide resin, and the pattern after development had an opening of 30 μm or more.

[0127] In Tables 1 and 2, the dielectric tangent values ​​obtained at 40 GHz and 10 GHz for Examples 1 to 24 were calculated using the following formula (i): x=(tan δ 40 -tan δ 10 ) / tan δ 10 (i) (where tan δ 40 indicates the dielectric tangent at a frequency of 40 GHz using the perturbation split cylinder resonator method, and tanδ 10 The value of x given by using the dielectric loss tangent at a frequency of 10 GHz measured by the perturbation split cylinder resonator method was 0.14 to 0.19, and was 0.25 in Comparative Example 1. As is clear from the results of Examples 1 and 24, the same results were obtained when cured films of different thicknesses were used. In Tables 1 and 2, the dielectric tangents of the cured films formed to a thickness of 10 μm in Examples 1 to 23 at 60 GHz and 10 GHz were calculated using the following formula (ii): x=(tan δ 60 -tan δ 10 ) / tan δ 10 (ii) (where tan δ 60 indicates the dielectric tangent at a frequency of 60 GHz using the perturbation split cylinder resonator method, and tanδ 10 The value of x given by using the formula (x=10 GHz dielectric tangent measured by the perturbation split cylinder resonator method) was 0.25 to 0.28, and was 0.34 in Comparative Example 1. As is clear from the results of Examples 1 and 24, the same results were obtained when cured films of different thicknesses were used.

[0128] Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the spirit of the invention. [Industrial Applicability]

[0129] The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials that are useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) Polyimide precursor: 100 parts by mass, (B) photosensitizer: 0.1 to 10 parts by mass, (C) a dielectric loss tangent reducing agent: 1 to 50 parts by mass, and (D) Solvent: 50 to 300 parts by mass wherein the (C) low dielectric tangent agent has a molecular weight of 100 to 3,500.

2. The (C) dielectric loss tangent reducing agent is represented by the following formula (I): 【Chemistry 1】 {In the formula, R １ and R ４ and R ５ are each independently a hydrogen atom, a methyl group, or a t-butyl group; R ２ and R ３ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms, and Z is an organic group having 7 to 80 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or an organic group having 2 to 15 carbon atoms and containing a carbonyl group. The photosensitive resin composition according to claim 1 , having a structure represented by the following formula:

3. The (C) dielectric loss tangent reducing agent is represented by the following formula (II): 【Chemistry 2】 {In the formula, R １ and R ４ and R ５ and R ６ and R ７ and R １０ are each independently a hydrogen atom, a methyl group, or a t-butyl group; R ２ and R ３ and R ８ and R ９ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms, and Z is a divalent organic group having 1 to 50 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a divalent organic group having 1 to 75 carbon atoms. The photosensitive resin composition according to claim 1 or 2, having a structure represented by the following formula:

4. The (C) dielectric loss tangent reducing agent is represented by the following formula (III): 【Chemistry 3】 {In the formula, R １ and R ４ and R ５ and R ６ and R ９ and R １０ and R １１ and R １２ and R １５ are each independently a hydrogen atom, a methyl group, or a t-butyl group; R ２ and R ３ and R ８ and R ７ and R １３ and R １４ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms, and Z is a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.} The photosensitive resin composition according to claim 1 or 2, having a structure represented by the following formula:

5. The photosensitive resin composition according to any one of claims 2 to 4, wherein Z has at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen.

6. (C) The dielectric loss tangent reducing agent is represented by the following formula: 【Chemistry 4】 {In the formula, Z is an organic group containing a carbonyl group and having 2 to 15 carbon atoms.} The photosensitive resin composition according to claim 1 or 2, having at least one structure represented by the following formula:

7. The (C) dielectric loss tangent reducing agent is represented by the following formula (IV): 【Chemistry 5】 {In the formula, R １ and R ４ and R ５ and R ６ and R ７ and R １０ and R １１ and R １２ and R １５ and R １６ and R １９ and R ２０ are each independently a hydrogen atom, a methyl group, or a t-butyl group; R ２ and R ３ and R ８ and R ９ and R １３ and R １４ and R １７ and R １８ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 50 carbon atoms, and Z is a tetravalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a tetravalent organic group having 1 to 50 carbon atoms.} The photosensitive resin composition according to claim 1 or 2, having a structure represented by the following formula:

8. The polyimide precursor (A) is represented by the following general formula (1): 【Chemistry 6】 {In formula (1), X １ is a tetravalent organic group having 6 to 40 carbon atoms; Y １ is a divalent organic group having 6 to 40 carbon atoms, n １ is an integer from 2 to 150; R １ and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. １ and R ２ At least one of the following general formula (2): 【Chemistry 7】 (In formula (2), R ３ , R ４ and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. It is a group represented by the following formula: The photosensitive resin composition according to any one of claims 1 to 7, wherein

9. The Y １ is represented by the following formula (Y1): 【Chemistry 8】 In the formula, each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, A represents an oxygen atom or a sulfur atom, and B represents a group represented by the following formula: 【Chemistry 9】 It is one of the following. The photosensitive resin composition according to claim 8 , wherein the photosensitive resin composition is represented by the formula:

10. The Y １ is expressed by the following formula: 【Chemistry 10】 Or the following formula: 【Chemistry 11】 Or the following formula: 【Chemistry 12】 The photosensitive resin composition according to claim 9 , wherein the structure is represented by the following formula:

11. The X １ is represented by the following formula (X1): 【Chemistry 13】 In the formula, each Ry independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, C represents an oxygen atom or a sulfur atom, and D represents a group represented by the following formula: 【Chemistry 14】 It is one of the following. The photosensitive resin composition according to any one of claims 8 to 10, wherein

12. The X １ is expressed by the following formula: 【Chemistry 15】 Or the following formula: 【Chemistry 16】 The photosensitive resin composition according to claim 11, wherein the structure is represented by the following formula:

13. The photosensitive resin composition according to any one of claims 1 to 12, wherein the (B) photosensitizer is a photoradical polymerization initiator.

14. The photosensitive resin composition according to any one of claims 1 to 13, which is a negative type photosensitive resin composition.

15. A method for producing a cured film obtained from a photosensitive resin composition comprising 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, the cured film being represented by the following formula (i): 0.001<(tanδ ４０ -tanδ １０ ) / tanδ １０ <0.2 (i) {In the formula, tanδ ４０ indicates the dielectric tangent at a frequency of 40 GHz by the perturbation type split cylinder resonator method, and tan δ １０ indicates a dielectric tangent at a frequency of 10 GHz as determined by a perturbation type split cylinder resonator method.

16. A method for producing a cured film obtained from a photosensitive resin composition comprising 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, the cured film being represented by the following formula (ii): 0.001<(tanδ ６０ -tanδ １０ ) / tanδ １０ <0.29 (ii) {In the formula, tanδ ６０ indicates the dielectric tangent at a frequency of 60 GHz by the perturbation type split cylinder resonator method, and tan δ １０ indicates a dielectric tangent at a frequency of 10 GHz as determined by a perturbation type split cylinder resonator method.

17. A method for producing a cured film obtained from a photosensitive resin composition comprising 100 parts by mass of a polyimide precursor, 0.1 to 10 parts by mass of a photosensitizer, and 50 to 300 parts by mass of a solvent, the cured film being represented by the following formulas (i) and (ii): 0.001<(tanδ ４０ -tanδ １０ ) / tanδ １０ <0.2 (i) 0.001<(tanδ ６０ -tanδ １０ ) / tanδ １０ <0.29 (ii) {In the formula, tanδ ４０ indicates the dielectric tangent at a frequency of 40 GHz by the perturbation type split cylinder resonator method, and tan δ １０ indicates the dielectric tangent at a frequency of 10 GHz by the perturbation type split cylinder resonator method, and tan δ ６０ indicates a dielectric tangent at a frequency of 60 GHz as determined by a perturbation type split cylinder resonator method.

18. The method for producing a cured film according to any one of claims 15 to 17, wherein the photosensitizer contained in the photosensitive resin composition is a photoradical polymerization initiator.

19. The method for producing a cured film according to any one of claims 15 to 18, wherein the photosensitive resin composition is a negative photosensitive resin composition.

20. The method for producing a cured film according to any one of claims 15 to 19, wherein the photosensitive resin composition contains an agent for reducing dielectric tangent.

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