Photosensitive resin composition

Abstract

To provide a photosensitive resin composition which exhibits a low dielectric loss tangent, is excellent in storage stability, has high resolution, and enables formation of a cured relief pattern.SOLUTION: A photosensitive resin composition contains 100 pts.mass of (A) a polyimide precursor represented by formula (1), 0.5-10 pts.mass of (B) a photosensitive agent, and 100-300 pts.mass of (D) a solvent, in which an imidization ratio of the photosensitive resin layer immediately before exposure obtained by removing a solvent from the photosensitive resin composition is 15-50%, and in polyimide of the polyimide cured film, an imide group concentration that is a ratio of an imide group per repeating unit is 12-30 wt.%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a negative-type photosensitive resin composition that exhibits a low dielectric loss tangent, has excellent storage stability, and is capable of forming a cured relief pattern with high resolution, a method for producing the same, and a method for producing a cured polyimide film using the negative-type photosensitive resin composition. [Background technology]

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

[0003] Semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards using various methods depending on the purpose. Conventional elements have generally been fabricated using wire bonding, which connects the external terminals (pads) of the element to the lead frame with thin wires. However, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has recently been proposed from the perspective of achieving high-speed transmission and thinner packages. FOWLP is a mounting technology in which a pre-processed wafer is diced to produce individual chips, the individual chips are reassembled on a support, sealed with molding resin, and a rewiring layer is formed after the support is peeled off.

[0004] In recent years, there has been an urgent need to develop packages for the new communications standard, the fifth-generation mobile communications system (5G). Unlike conventional 4G technology, 5G uses millimeter-wave (10 GHz to 80 GHz) frequency bands, enabling high-speed, large-capacity communications, low signal latency, and simultaneous connection of multiple terminals, which were not possible with conventional communications. In the millimeter-wave band, transmission loss in signal wiring on printed wiring boards is highly affected, raising concerns about heat generation and transmission delays. To reduce transmission loss, antenna-in-package (AiP) devices have been developed that integrate the front-end module (FEM) that transmits and receives radio waves with the antenna (see, for example, Patent Document 1 below). Because AiPs use short wiring lengths, they can suppress transmission loss, which increases in proportion to the wiring length. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] US Patent Application Publication No. 2016 / 0104940 Summary of the Invention [Problem to be solved by the invention]

[0006] On the other hand, there are limits to suppressing transmission loss through package design, and improvements are also needed in terms of materials. If the dielectric constant or dielectric dissipation factor (tanδ) of the insulating material used to form the wiring is high, the dielectric loss increases, resulting in an overall increase in transmission loss. While polyimides have excellent insulating performance and film properties, the imide group itself is a polar functional group. Furthermore, photosensitive polyimide precursor compositions contain many polar compounds, such as photopolymerization initiators and crosslinking agents, resulting in high dielectric constants and dielectric dissipation factors, and a need for reduced dielectric properties.

[0007] In view of the current state of the art, an object of the present invention is to provide a negative-type photosensitive resin composition that exhibits a low dielectric loss tangent, has excellent storage stability, and is capable of forming a cured relief pattern with high resolution, a method for producing the same, a polyimide cured film using the photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device having the cured relief pattern.

[0008] The present inventors unexpectedly found that the above-mentioned problems can be solved by adjusting the properties of a photosensitive resin composition containing a polyimide precursor, and have completed the present invention. That is, the present invention is as follows.

[0009] [1] (A) The following general formula (1): [ka] In the formula, 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 of 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] (wherein R3, R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.) 100 parts by mass of a polyimide precursor represented by the formula: (B) photosensitizer: 0.5 to 10 parts by mass; and (D) Solvent: 100~300 parts by mass; A photosensitive resin composition comprising: a photosensitive resin layer before exposure obtained by removing the solvent from the photosensitive resin composition; and a peak at 1380 cm in an infrared absorption spectrum measured by an ATR (Attenuated Total Reflection) method. -1 The peak intensity near 1500cm -1a photosensitive resin composition in which an imidization rate b, which is the value obtained by dividing the imidization index of the photosensitive resin layer, obtained by dividing the peak intensity near the peak, by the imidization index of a cured film obtained by heating and curing the photosensitive resin composition at 350°C, is 15% to 50%, and an imide group concentration a, which is the proportion of imide groups to the molecular weight of a repeating unit containing a structure derived from tetracarboxylic acid and diamine, in the polyimide of the cured polyimide film, is 12 wt% to 30 wt%. [2] The imide group concentration a and the imidization rate b are expressed by the following formula (1): 0.10 ≦ a ×(1-b) ≦ 0.17 ...(1) The photosensitive resin composition according to [1] above, which satisfies the above. [3] The photosensitive resin composition according to [1] or [2], wherein the polyimide of the polyimide cured film has an imide group concentration a, which is the proportion of imide groups to the molecular weight of a repeating unit containing a structure derived from a tetracarboxylic acid and a diamine, of 12 wt % to 24 wt %. [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the polyimide cured film obtained by heating and curing at 350° C. has an imidization index of 0.10 to 0.54. [5] The photosensitive resin composition according to any one of [1] to [4] above, wherein the photosensitive resin layer formed by applying the photosensitive resin composition to quartz glass and heating it at 110°C for 3 minutes has an absorbance at 365 nm per μm of 0.02 to 0.09. [6] In the general formula (1), Y1 is represented by the following formula: [ka] In the formula, each Rz is independently a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a is an integer of 0 to 4, A is an oxygen atom or a sulfur atom, and B is a group represented by the following formula: [ka] The photosensitive resin composition according to any one of the above [1] to [5], which is represented by the formula: [7] wherein Y1 is a group represented by the following formula: [ka] or [ka] or [ka] The photosensitive resin composition according to [6] above, wherein the photosensitive resin composition is represented by the following formula: [8] X1 in the general formula (1) is the following formula: [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] The photosensitive resin composition according to any one of the above [1] to [7], which is represented by the formula: [9] wherein X1 is represented by the following formula: [ka] or [ka] The photosensitive resin composition according to [8] above, wherein the photosensitive resin composition is represented by the formula:

[10] The photosensitive resin composition is negative-type and contains (A) 50 to 85 parts by mass of a polyimide precursor, (B) 0.5 to 10 parts by mass of a photosensitizer, and (D) 100 to 300 parts by mass of a solvent, and contains 15% by mass to 50% by mass of the polyimide precursor, and the polyimide precursor is represented by the following general formula (11): [ka] {wherein X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.}

[11] The photosensitive resin composition is negative-type and contains (A) 50 to 85 parts by mass of a polyimide precursor, (B) 0.5 to 10 parts by mass of a photosensitizer, and (D) 100 to 300 parts by mass of a solvent, and the polyimide precursor is contained in an amount of 15 to 50% by mass, and the polyimide precursor is a polyimide precursor represented by the general formula (1) and a compound represented by the following general formula (11): [ka] {wherein X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.}

[12] (C) at least one organic compound selected from an organic titanium compound or an organic zirconium compound: 0.01 to 5 parts by mass; The photosensitive resin composition according to any one of [1] to

[11] above, further comprising:

[13] The photosensitive resin composition according to

[12] above, wherein the organic compound (C) is an organic titanium compound.

[14] The photosensitive resin composition according to

[12] or

[13] , wherein the organotitanium compound is at least one compound selected from the group consisting of tetraalkoxytitanium compounds, titanium chelate compounds, titanium acylate compounds, and titanocene compounds.

[15] The photosensitive resin composition according to

[14] above, wherein the organotitanium compound is a titanium chelate or tetraalkoxytitanium having two or more alkoxy groups.

[16] The photosensitive resin composition according to any one of [1] to

[15] above, which is used for forming an interlayer insulating film for a rewiring layer.

[17] (E) Monomer: 0.5 to 15 parts by mass; The photosensitive resin composition according to any one of [1] to

[16] above, further comprising:

[18] The photosensitive resin composition according to

[17] above, wherein the (E) monomer contains at least one group selected from the group consisting of a hydroxy group and an amino group.

[19] the steps of: a step of mixing the (A) polyimide precursor, the (B) photosensitizer, and the (D) solvent; and a step of aging the obtained mixture at 23°C to 50°C for 24 hours to 360 hours to adjust the imidization rate to 15% to 50%;

[19] A method for producing the photosensitive resin composition according to any one of [1] to

[18] above, comprising:

[20] Steps (1) to (5) below: (1) a step of applying the photosensitive resin composition according to any one of the above items [1] to

[17] onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer; (3) a step of exposing the photosensitive resin layer after heating and drying; (4) developing the exposed photosensitive resin layer; and (5) a step of heat-treating the developed photosensitive resin layer to form a cured polyimide film; A method for producing a cured polyimide film, comprising:

[21] The method for producing a cured polyimide film according to

[20] above, wherein the cured polyimide film has a dielectric loss tangent of 0.0021 to 0.007 when measured at 10 GHz by a perturbation split cylinder resonator method.

[22] The method for producing a cured polyimide film according to

[20] or

[21] above, wherein the cured polyimide film has a dielectric loss tangent of 0.0021 to 0.008 when measured at 28 GHz by a perturbation split cylinder resonator method.

[23] The method for producing a cured polyimide film according to any one of

[20] to

[22] above, wherein the cured polyimide film has a dielectric loss tangent of 0.0021 to 0.008 when measured at 40 GHz by a perturbation split cylinder resonator method.

[24] The method for producing a cured polyimide film according to any one of

[20] to

[23] above, wherein the cured polyimide film has a dielectric loss tangent of 0.0021 to 0.009 when measured at 60 GHz by a perturbation split cylinder resonator method.

[25] (A) The following general formula (1): [ka] In the formula, 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 of 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] (wherein R3, R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.) 100 parts by mass of a polyimide precursor represented by the formula: (B) photosensitizer: 0.5 to 10 parts by mass; and (D) Solvent: 100~300 parts by mass; A method for producing a cured polyimide film using a photosensitive resin composition comprising the following steps (1) to (5): (1) applying the photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer to remove the solvent; (3) a step of exposing the photosensitive resin layer from which the solvent has been removed; (4) developing the exposed photosensitive resin layer; and (5) a step of heat-treating the developed photosensitive resin layer to form a cured polyimide film; wherein the imidization rate of the photosensitive resin layer before exposure obtained by removing the solvent after heating and drying in step (2) is 15 to 50%. [Effects of the Invention]

[0010] The photosensitive resin composition according to the present invention can be used to produce a cured resin film having an excellent dielectric loss tangent while maintaining the resolution of the relief pattern in a thick film. In one embodiment, by increasing the imidization rate of the photosensitive resin layer obtained from the photosensitive resin composition within a predetermined range, polar compounds derived from the side chains of the polyimide precursor are easily removed in a heating step, and the resulting cured film can have a low dielectric loss tangent and a small frequency dependency. Furthermore, by adjusting the absorbance of the photosensitive resin layer obtained from the photosensitive resin composition within a predetermined range, the resolution of the relief pattern in a thick film can be maintained. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be practiced with various modifications within the scope of the gist thereof. Throughout this specification, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they are each independently selected unless otherwise specified, and may be the same or different from each other. Furthermore, structures represented by the same symbol in different general formulas are also each independently selected unless otherwise specified, and may be the same or different from each other.

[0012] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment contains (A) a polyimide precursor, (B) a photosensitizer (photopolymerization initiator), and (D) a solvent, and may optionally further contain (C) an organic compound such as a titanium or zirconium compound, (E) a monomer, or other components. Each component will be explained in turn below. The photosensitive resin composition is preferably a negative type from the viewpoint of the physical properties of the polyimide precursor A) described below.

[0013] The photosensitive resin composition preferably used in the present invention has an absorbance at 365 nm (i-line) of 0.02 to 0.09 per μm. The i-line absorbance of a 1 μm-thick film can be measured using a standard spectrophotometer after pre-baking a coating of the photosensitive polyimide precursor alone on quartz glass. If the thickness of the formed film is not 1 μm, the i-line absorbance of the film can be calculated by converting the absorbance measured for the film to a 1 μm thickness according to the Beer-Lambert law. The i-line absorbance is preferably 0.04 or more, and from the viewpoint of suppressing reflected light, it is even more preferably 0.05 or more. Reflected light is light that is not absorbed in the film but travels to the bottom of the film and is reflected by the substrate, leading to pattern defects. If the i-line absorbance is 0.09 or less, light reaches the bottom of the photosensitive resin layer, and the difference in solubility between the soluble and insoluble parts can be maintained.

[0014] [(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 the formula, 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 of 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] (wherein R3, R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.) The polyamide has a structural unit represented by the following formula: R1 and R2 in general formula (1) are also referred to as side chains or side chain structures of the polyimide precursor.

[0015] In the general formula (1), n1 is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoint of the photosensitivity 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 or an alicyclic aliphatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are located at the ortho positions relative to each other. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (20): [ka] [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 fluorinated hydrocarbon group, l is an integer of 0 to 2, m is an integer of 0 to 3, and n is an integer of 0 to 4.} However, the X1 structure may be one type or a combination of two or more types. The X1 group having the structure represented by formula (20) is particularly preferred in that it achieves both heat resistance and photosensitivity.

[0017] 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 general formula (21): [ka] [ka] {In formula (21), 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 fluorinated hydrocarbon group, m is an integer of 0 to 3, and n is an integer of 0 to 4.} However, the examples are not limited to these. Furthermore, the structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by formula (21) is particularly preferred in that it achieves both heat resistance and photosensitive properties.

[0018] As the Y1 group, among the structures represented by the above formula (21), particularly, those represented by the following formula: [ka] [ka] The structure represented by the formula: {wherein 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 fluorinated hydrocarbon group, m is an integer of 0 to 3, and n is an integer of 0 to 4} is preferred from the viewpoints of low dielectric tangent, low dielectric constant, and lithographic properties.

[0019] In the 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 photosensitivity. Also, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitivity.

[0020] In this specification, the term "imide group concentration" refers to the mass ratio of imide groups to the molecular weight of repeating units containing structures derived from tetracarboxylic acid and diamine in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition according to this embodiment. In this specification, the term "polyimide precursor" includes polyimide precursors that are partially imidized. In this embodiment, the imide group concentration of the resulting cured polyimide film is 12 wt% to 30 wt%, preferably 12 wt% to 24 wt%. If the imide group concentration is 12 wt% or more, the adhesion between the mold resin and the cured relief pattern tends to be good. The imide group concentration is preferably 12.5 wt% or more, and more preferably 13.5 wt% or more. On the other hand, if the imide group concentration is 30 wt% or less, the dielectric loss tangent of the resulting cured polyimide film tends to be good. The imide group concentration is more preferably 23.0 wt% or less, and even more preferably 21.0 wt% or less.

[0021] The imide group concentration per repeating unit of the polyimide can be calculated using the molecular weights of the tetracarboxylic acid and diamine used in preparing the polyimide precursor according to the following formula (I): 70.02×2 / [Mw(A)+Mw(B)]×100 (I) {In formula (I), Mw(A) represents the molecular weight of the tetracarboxylic acid, and Mw(B) represents the molecular weight of the diamine.} When two or more types of tetracarboxylic acids and / or diamines are used, for example, when preparing using two types of tetracarboxylic acids and / or diamines, the molecular weight of the diamine is calculated by the following formula (II): 70.02×2 / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2]×100 (II) {In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic acid, Mw(A2) represents the molecular weight of the second tetracarboxylic acid, a1 represents the content of the first tetracarboxylic acid, a2 represents the content of the second tetracarboxylic acid, Mw(B1) represents the molecular weight of the first diamine, Mw(B2) represents the molecular weight of the second diamine, b1 represents the content of the first diamine, and b2 represents the content of the second diamine, provided that a1, a2, b1, and b2 satisfy the relationships a1+a2=1 and b1+b2=1, respectively.} The same calculation can be performed when three or more types of tetracarboxylic acids and / or diamines are used. When tetracarboxylic dianhydride is used as a raw material, the calculation is performed in terms of tetracarboxylic acid.

[0022] The cured film obtained from the photosensitive resin composition was measured by the ATR method. -1 and 1500cm -1 The peak intensity ratio (imidization index of the cured film) is determined by the aromatic ring (1500 cm -1 ) to the imide group (1380cm -1 In this embodiment, X1 and Y1 in general formula (1) are preferably selected from structures in which the imidization index of the cured film is 0.10 to 0.54, and from the viewpoint of low dielectric loss tangent, it is preferably 0.10 to 0.53, and from the viewpoint of lithography properties, it is more preferably 0.35 to 0.53.

[0023] (A) Preparation of polyimide precursor The polyimide precursor having the structure represented by the general formula (1) in this embodiment can be obtained, for example, by a method comprising: reacting a tetracarboxylic acid dianhydride having 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); and subsequently polycondensing the obtained acid / ester with a diamine having the divalent organic group Y1 having 6 to 40 carbon atoms.

[0024] (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, 4,4'-(4,4'-isopropylidenediphenoxy)acid dianhydride, etc. These may be used alone or in combination of two or more.

[0025] (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.

[0026] 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 and R2 in general formula (1). When the content of the organic group of general formula (2) exceeds 50 mol %, desired photosensitive properties can be obtained, which is preferable. 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 and R2 in general formula (1).

[0027] 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 the half-esterification reaction of the acid dianhydride proceeds to give the desired acid / ester. The reaction is preferably carried out at a reaction temperature of 20 to 50°C, with stirring for 4 to 10 hours.

[0028] The reaction solvent is preferably one that dissolves the acid / ester compound and the polyimide precursor, which is a polycondensation product of the acid / ester compound and a diamine. Examples of reaction solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 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 solvents may be used alone or in combination as needed.

[0029] (Preparation of Polyimide Precursor) A known dehydration condensation agent is mixed with the acid / ester compound (typically a solution in the reaction solvent) under ice cooling to convert the acid / ester compound 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 resulting mixture to polycondense, thereby obtaining a polyimide precursor. Examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

[0030] 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)pheny phenyl] sulfone, 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 ... bis(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl}propane, bis{4-(4-aminophenoxy)phenyl}ketone, and compounds in which a part of the hydrogen atoms on the benzene ring is substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,Examples of diamines include 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-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.

[0031] In order to improve the adhesion between the photosensitive resin layer formed on a substrate by applying the photosensitive resin composition of this 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 the preparation of the (A) polyimide precursor.

[0032] After the polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution may be filtered off as needed, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof may be added to the reaction solution to precipitate the polymer component. The polymer may be further purified by repeating the redissolution and reprecipitation procedures. The polymer may then be vacuum-dried to isolate the polyimide precursor. 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 an appropriate organic solvent to remove ionic impurities.

[0033] The molecular weight of the (A) polyimide precursor, as measured by gel permeation chromatography (GPC) 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. A weight average molecular weight of 8,000 or more is preferred because it provides good mechanical properties, while a weight average molecular weight of 150,000 or less is preferred because it provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0034] In the photosensitive resin composition using the (A) polyimide precursor, a part of the (A) polyimide precursor is imidized in the resin composition by a compound contained in the photosensitive resin composition and / or during the production process of the photosensitive resin composition. In this embodiment, the imidization rate of the polyimide precursor (A) in the resin composition is 15% to 50%, preferably 15% to 40%, when measured by the ATR method, from the viewpoints of low dielectric tangent, absorbance, and resolution. The absorbance of the polyimide precursor correlates with the imidization rate, and the absorbance also increases as the imidization rate increases. In this specification, the term "imidization rate" refers to the rate at which the imidization rate is increased at 1380 cm in the infrared spectrum. -1 The peak intensity at 1500cm -1 The imidization index of the photosensitive resin layer is calculated by dividing the value obtained by dividing the peak intensity of the photosensitive resin composition by the "imidization index of the cured film" obtained by curing the photosensitive resin composition at 350°C. When the polyimide precursor is imidized, a ring-closing reaction occurs, and the side chains corresponding to R1 and R2 in general formula (1) are eliminated and dispersed in the resin composition. In this embodiment, a portion of the polyimide precursor in the photosensitive resin composition is imidized, and the side chains are already dispersed in the resin composition before heat curing. Therefore, the methacrylate concentration in the resin composition remains unchanged, making it possible to maintain lithographic properties. Meanwhile, the methacrylate is easily volatilized by heating in the heat curing step, making it possible to reduce the amount of polar compounds remaining in the cured film.

[0035] From the viewpoint of low dielectric loss tangent and absorbance, the imide group concentration a and the imidization rate b are expressed by the following formula (1): 0.10 ≦ a ×(1-b) ≦ 0.17 ...(1) It is preferable to satisfy the following. Without being bound by theory, when a × (1 - b) is in the range of 0.1 to 0.17, the amount of polyimide precursor side chains remaining in the cured polyimide film is reduced, resulting in a low dielectric loss tangent. In addition, the absorbance, which increases as the imidization proceeds, can be kept below a certain value.

[0036] [(B) Photosensitizer] The photosensitive resin composition of this embodiment contains a photosensitizer. In one embodiment, the photosensitizer may be a photopolymerization initiator. The photopolymerization initiator is preferred because it promotes curing of the relief pattern by light irradiation. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples thereof include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl 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-methoxyphenyl)-2-methyl-2-methylpropiophenone; 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. The amount of the photopolymerization initiator is 0.5 to 10 parts by mass, and preferably 1 to 8 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor. The amount is 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning ability, 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.

[0037] [(C)Organic compound] In this embodiment, the photosensitive resin composition may contain an organic compound (C). The organic compound (C) preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. The organic group preferably contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. By containing the organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases. Usable organic titanium or zirconium compounds include, for example, those in which an organic group is bonded to a titanium or zirconium atom via a covalent bond or an ionic bond.

[0038] Specific examples of the organic titanium or zirconium compounds are shown below in I) to VII): I) As the chelate compound, a compound having two or more alkoxy groups is more preferred because it improves the storage stability of the photosensitive resin composition and enables the formation of good patterns. Specific examples of the 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), and compounds in which the titanium atom of these compounds is substituted with a zirconium atom, but are not limited thereto.

[0039] II) Examples of tetraalkoxy 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, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and compounds in which the titanium atom of these compounds is substituted with a zirconium atom, but are not limited to these.

[0040] III) Examples of titanocene or zirconocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 Examples of the titanium-containing compound include, but are not limited to, bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds in which the titanium atom in these compounds is replaced with a zirconium atom.

[0041] IV) Examples of monoalkoxy compounds include, but are not limited to, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, and compounds in which the titanium atom of these compounds is substituted with a zirconium atom.

[0042] V) Examples of titanium oxide or zirconium oxide compounds include, but are not limited to, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and compounds in which the titanium atom of these compounds is substituted with a zirconium atom.

[0043] VI) Examples of titanium tetraacetylacetonate or zirconium tetraacetylacetonate compounds include, but are not limited to, titanium tetraacetylacetonate and compounds in which the titanium atom of these compounds is substituted with a zirconium atom.

[0044] VII) Examples of titanate coupling agents include, but are not limited to, isopropyl tridodecylbenzenesulfonyl titanate.

[0045] 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 I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting a better dielectric tangent. 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.

[0046] When an organic titanium or zirconium compound is blended, the blending amount is 0.01 to 5 parts by mass, and preferably 0.1 to 3 parts by mass, per 100 parts by mass of the (A) resin. If the blending amount is 0.01 part by mass or more, a good imidization rate of the resin composition and a good dielectric loss tangent of the cured film are exhibited, while if the blending amount is 10 parts by mass or less, excellent storage stability is achieved, which is preferable.

[0047] The photosensitive resin composition of this embodiment contains the organic compound (C) described above, which can improve the imidization rate of the polyimide precursor contained in the resin composition and reduce the dielectric loss tangent of a cured film using the resin composition. Without being bound by theory, it is believed that the reason for improving the imidization rate of the polyimide precursor is that the metal element contained in the organic compound (C) coordinates to the carbonyl group derived from the ester group and / or carboxyl group of the polyimide precursor, thereby reducing the electron density of the carbon atom of the carbonyl group and promoting the ring-closing reaction. The reason for the decrease in the dielectric loss tangent is that the ring-closing reaction partially proceeds before the heat treatment for curing the resin composition, resulting in the formation of a ring-closing compound represented by the following general formula (1): [ka] {wherein 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.} This is thought to be because R1 and / or R2 in the polyimide precursor are eliminated from the polymer structure upon ring closure of the polyimide precursor, making them more likely to volatilize during the heating step in the cured film production process. In addition, if R1 and / or R2 contain a polymerizable functional group, they remain in the film during the exposure step in the cured film production process, and therefore the concentration of polymerizable functional groups in the film does not change even if the imidization rate increases, and therefore resolution is not affected.

[0048] [(D) Solvent] The photosensitive resin composition of this embodiment contains (D) a solvent (also referred to as a solvent). From the viewpoint of solubility in (A) the polyimide precursor, it is preferable to use a polar organic solvent as the solvent. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and 2-octanone. These may be used alone or in combination of two or more.

[0049] In this embodiment, the amount of the (D) solvent is in the range of 100 to 300 parts by mass per 100 parts by mass of the (A) polyimide precursor, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0050] From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol is preferred. Suitable usable alcohols are typically alcohols having an alcoholic hydroxyl group in the molecule but not 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 ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are particularly preferred.

[0051] 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, and more preferably 10% by mass to 30% by mass, based on the mass of the total solvent. If the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, while if it is 50% by mass or less, the solubility of the (A) polyimide precursor is improved.

[0052] [(E) Monomer] In this embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain a (E) monomer having a photopolymerizable unsaturated bond. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator. Examples of such a monomer include, but are not limited to, mono- or diacrylates or methacrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates or methacrylates of propylene glycol or polypropylene glycol, mono-, di-, or triacrylates or methacrylates of glycerol, cyclohexane diacrylate or dimethacrylate, diacrylate or dimethacrylate of 1,4-butanediol, and 1,6 Examples of suitable monomers include diacrylate or dimethacrylate of 1-hexanediol, diacrylate or dimethacrylate of neopentyl glycol, mono- or diacrylate or methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate or methacrylate, acrylamide or a derivative thereof, methacrylamide or a derivative thereof, trimethylolpropane triacrylate or methacrylate, di- or triacrylate or methacrylate of glycerol, di-, tri-, or tetraacrylate or methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds. These monomers may be used alone or in a mixture of two or more.

[0053] When the resin composition is aged, the polyimide precursor contained in the resin composition undergoes ring closure, resulting in the elimination of side chain molecules. The eliminated side chain molecules can exist as monomers in the resin composition. The monomer preferably has at least one group selected from a hydroxy group and an amino group, and more preferably has a group represented by the following general formula (3): [ka] A structure represented by the following formula is preferred: {In formula (3), Z is at least one group selected from the group consisting of a hydroxy group and an amino group, R7, R8, and R9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10.}

[0054] In this embodiment, the blending amount of the monomer having a photopolymerizable unsaturated bond is 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0055] [Other ingredients] The photosensitive resin composition of this embodiment may further contain components other than the above components (A) to (E). Examples of such components include resin components other than the polyimide precursor (A), a sensitizer, a monomer having a photopolymerizable unsaturated bond, a bonding aid, a thermal polymerization inhibitor, an azole compound, and a hindered phenol compound.

[0056] In one embodiment, the photosensitive resin composition may further contain a resin component other than (A) the polyimide precursor. Examples of resin components that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The amount of these resin components to be added is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of (A) the polyimide precursor.

[0057] When a positive-type photosensitive resin composition is prepared using a polyoxazole precursor together with (A) a polyimide precursor, a compound having a quinone diazide group, such as a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, may be used in combination as a positive-type photosensitive material.

[0058] In one embodiment, the photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindano. p-Dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combination of two or more (for example, two to five types). The amount of the sensitizer to be added is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

[0059] In one embodiment, the photosensitive resin composition may optionally contain an adhesion promoter to improve adhesion between a film formed using the photosensitive resin composition and a 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, and N-[3-(triethoxysilyl)propyl]phthalate. Examples of suitable adhesives include silane coupling agents such as amide 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, as well as aluminum-based adhesive aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate. These adhesive aids may be used alone or in combination of two or more.

[0060] Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesive strength. The amount of the adhesion aid to be added is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0061] In one embodiment, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the viscosity and photosensitivity stability of the photosensitive resin composition, particularly during storage in a solvent-containing solution. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, 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. These thermal polymerization inhibitors may be used alone or in combination. The amount of the thermal polymerization inhibitor to be added is preferably in the range of 0.005 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 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. Examples of benzotriazole include 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, and 1-methyl-1H-tetrazole. 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 (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity. If the amount of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of the (A) polyimide precursor, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while if the amount is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0064] In this embodiment, the photosensitive resin composition may contain a hindered phenol compound to suppress discoloration on copper. 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), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol). 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-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(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) benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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 suitable hydroxyl groups include, but are not limited to, riazine-2,4,6-(1H,3H,5H)-trione, 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. 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 (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity. If the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the (A) polyimide precursor, 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 if the amount is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0066] The photosensitive resin composition of the present embodiment can be prepared by the following steps: a step of mixing the (A) polyimide precursor, the (B) photosensitizer, and the (D) solvent; and a step of aging the obtained mixture at 23°C to 50°C for 24 hours to 360 hours to adjust the imidization rate to 15% to 50%; The composition can be produced by a production method including the steps of: "Aging" is a process in which the photosensitive resin composition is left standing at a certain temperature for a certain period of time. The aging temperature is 23°C to 50°C, and preferably 30 to 50°C. The aging time is 24 hours to 360 hours, and preferably 48 hours to 280 hours. By such aging, the photosensitive resin composition can be degassed, and the imidization rate of the (A) polyimide precursor in the photosensitive resin composition can be adjusted to a predetermined range.

[0067] [Polyimide] The polyimide contained in the cured relief pattern formed from the polyimide precursor composition is 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 reasons, the preferred X1 and Y1 in general formula (1) are also preferred in the polyimide of general formula (11). The number m of repeating units in general formula (11) is not particularly limited, but can be an integer of 2 to 150.

[0068] [Cured film and method for producing the same] Another embodiment of the present invention is a method for producing a cured polyimide film, which includes a step of converting the above-described photosensitive resin composition into a polyimide. That is, the method for producing a polyimide cured film of the present embodiment includes the following steps (1) to (5): (1) a step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer; (3) a step of exposing the photosensitive resin layer after heating and drying; (4) developing the exposed photosensitive resin layer; and (5) a step of heat-treating the developed photosensitive resin layer to form a cured polyimide film; It includes: In another embodiment of the present invention, there is provided a cured polyimide film obtained from the photosensitive resin composition described above, and a method for producing the same. The cured film preferably has a dielectric loss tangent of 0.0021 to 0.007, more preferably 0.0030 to 0.0065, when measured at 10 GHz using a perturbation split cylinder resonator method. The dielectric loss tangent measured at 28 GHz is preferably 0.0021 to 0.008, and from the viewpoint of frequency dependence, more preferably 0.0030 to 0.0075. The dielectric loss tangent measured at 40 GHz is preferably 0.0021 to 0.008, and from the viewpoint of frequency dependence, more preferably 0.0030 to 0.0075. The dielectric loss tangent measured at 60 GHz is preferably 0.0021 to 0.009, and from the viewpoint of frequency dependence, more preferably 0.0030 to 0.0085. The dielectric loss tangent can be measured by a perturbation type split cylinder resonator method shown in the examples below.

[0069] The photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitizer, and 100 to 300 parts by mass of a solvent, more preferably contains a photoradical polymerization initiator as the photosensitizer, and further preferably the photosensitive resin composition is negative.

[0070] Specific steps in the method for producing a cured film can be carried out in accordance with steps (1) to (5) of the method for producing a cured film described above.

[0071] Each step will be described below. [(1) Step of applying the photosensitive resin composition 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 to a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0072] [(2) Step of heating and drying the obtained photosensitive resin layer] If necessary, the coating film made of the photosensitive resin composition can be dried. Examples of drying methods include air drying, heat drying using an oven or hot plate, and vacuum drying. It is desirable 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 at 20°C to 140°C for 1 minute to 1 hour. A photosensitive resin layer can be formed on the substrate in this manner.

[0073] [(3) Step of exposing the photosensitive resin layer after heating and drying] In this process, the photosensitive resin layer that has undergone the above process (2) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0074] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary. The baking conditions range from a temperature of 40°C to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as the properties of the negative-type photosensitive resin composition are not impaired. The imidization ratio of the polyimide precursor remains unchanged before and after baking.

[0075] [(4) Step of developing the exposed photosensitive resin layer] In this step, the exposed photosensitive resin layer is developed to form a relief pattern. In this step, when the photosensitive resin composition is negative, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be any of the conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern. The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Examples of suitable good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. 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 depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination.

[0076] [(5) Step of heat-treating the developed photosensitive resin layer to form a cured polyimide film] In this step, the relief pattern obtained by the development is heated to dissolve the photosensitive component and imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern made of polyimide. Heat curing can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 150°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon.

[0077] [Semiconductor Devices] A semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern using the photosensitive resin composition of this embodiment can also be provided. Therefore, 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-described method for producing a cured relief pattern. Another embodiment can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-described method for producing a cured relief pattern as part of its process. The semiconductor device of this embodiment can be produced by forming the cured relief pattern formed by the above-described 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.

[0078] [Display device] The photosensitive resin composition of this embodiment can also be used to provide a display device comprising a display element and a cured film disposed on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated directly on the display element, or may be laminated via another layer. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0079] The photosensitive resin composition of the present embodiment is useful not only for application to the semiconductor device described above, but also for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Example]

[0080] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin compositions were measured and evaluated according to the following methods.

[0081] [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 was a "Shodex 805M / 806M series" column 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.

[0082] (2) Measurement of the imidization index of the cured film A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering system (L-440S-FHL, Canon Anelva Corporation). A photosensitive resin composition prepared by the method described below was then spin-coated onto the wafer using a coater developer (D-Spin60A, SOKUDO Co., Ltd.) and dried by heating on a hot plate at 110°C for 3 minutes, forming a photosensitive resin layer approximately 15 μm thick. Using a test pattern mask, this photosensitive resin layer was irradiated with 200 mJ / cm2 using a Prisma GHI (Ultratech Co., Ltd.) equipped with an i-line filter. 2 was irradiated with energy of The wafer with the relief pattern formed on Cu was heat-treated in a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg) at 350°C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern made of resin approximately 10 μm thick on Cu. The cured relief pattern was measured using an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) with a Si prism, and the measurement range was 4000 to 700 cm -1 The measurement was carried out 50 times. -1 Around (1350~1450cm -1(If there are multiple peaks, the peak with the highest intensity) and 1500 cm -1 Around (1460~1550cm -1 The peak intensity was calculated by determining the peak height of the peak with the greatest intensity (if there are multiple peaks, the peak with the greatest intensity).

[0083] (3) Measurement of imidization rate of photosensitive resin composition The photosensitive resin composition prepared by the method described below was spin-coated onto a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a coater developer (D-Spin60A, SOKUDO Co., Ltd.), and then heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer approximately 10 μm thick. The photosensitive resin layer was measured using an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) with a Si prism, and the measurement range was 4000 to 700 cm -1 The measurement was carried out 50 times. -1 Around (1350~1450cm -1 (If there are multiple peaks, the peak with the highest intensity) and 1500 cm -1 Around (1460~1550cm -1 The imidization index of the photosensitive resin layer was calculated by dividing the imidization index of the photosensitive resin layer of each of the resin compositions of the Examples and Comparative Examples by the imidization index of a cured film obtained by curing the resin composition at 350°C.

[0084] (4) Resolution of hardened relief patterns on Cu A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering system (L-440S-FHL, Canon Anelva Corporation). A photosensitive resin composition prepared by the method described below was then spin-coated onto the wafer using a coater developer (D-Spin60A, SOKUDO Co., Ltd.) and dried by heating on a hot plate at 110°C for 3 minutes, forming a photosensitive resin layer approximately 25 μm thick. Using a test pattern mask, this photosensitive resin layer was irradiated with 200 mJ / cm2 using a Prisma GHI (Ultratech Co., Ltd.) equipped with an i-line filter. 2 The photosensitive resin layer was then spray-developed with a coater developer (D-Spin 60A, 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-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg) at 230°C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern made of resin approximately 20 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 in the pattern obtained was at least half the area of ​​the corresponding opening in the pattern mask, the pattern was deemed resolved, and the resolution was evaluated according to the following criteria based on the length of the mask opening side corresponding to the smallest area among the resolved openings (the size of the opening pattern). (Evaluation criteria) "Excellent": The minimum opening pattern size is less than 25 μm "Good": The minimum opening pattern size is 25 μm or more and less than 30 μm "Acceptable": The minimum opening pattern size is 30 μm or more and less than 35 μm "Not acceptable": The minimum opening pattern size is 35 μm or more.

[0085] (5) Measurement of relative permittivity (Dk) and dielectric loss tangent (Df) A 100 nm thick aluminum (Al) wafer substrate was prepared by sputtering a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering system (L-440S-FHL, Canon Anelva Corporation). The negative photosensitive resin composition was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin 60A, manufactured by SOKUDO Co., Ltd.), and then heated and dried at 110°C for 180 seconds to produce a spin-coated film. The film was then dried at an exposure dose of 600 mJ / cm2 using an aligner (PLA-501F, manufactured by Canon Co., Ltd.). 2 The entire surface was exposed to ghi rays, and then subjected to a heat curing treatment at 230°C for 2 hours 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 80 mm long and 60 mm wide or 40 mm long and 30 mm wide pieces 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.

[0086] The relative permittivity (Dk) and dielectric loss tangent (Df) of the film sample were measured 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: approximately 10 GHz), CR-728 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 28 GHz), CR-740 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 40 GHz), CR-760 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 60 GHz)

[0087] (6) Absorbance The negative photosensitive resin composition was spin-coated onto a quartz glass sheet (50 mm long, 50 mm wide, 1 mm thick) using a manual spin coater (ELS306MA, manufactured by SEBACS) and dried by heating at 110°C for 180 seconds to produce a spin-coated film. The rotation speed of the manual spin coater was set so that the spin-coated film would be 10 µm thick. The spin-coated films were measured using an ultraviolet-visible (UV-VIS) spectrophotometer (UV-1800, Shimadzu Corporation). The absorbance at 365 nm was measured and converted to 1 μm according to the Beer-Lambert law.

[0088] [(A) Preparation of Polyimide Precursor] <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 generated by the reaction had ceased, the mixture was allowed to cool to room temperature and then left to stand for a further 16 hours.

[0089] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by a suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 ml of γ-butyrolactone with stirring over 60 minutes. 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 that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0090] The resulting reaction solution 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 resulting crude polymer solution was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM15") to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and dried in vacuum to obtain powdery polymer A-1. The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 22,000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-1 was 27.4 wt %.

[0091] <Production Example 2> (Synthesis of Polyimide Precursor (Polymer A-2)) Polymer A-2 was obtained by carrying out a 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. The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 24,000.The imide group concentration per repeating unit of the polyimide obtained from polymer A-2 was 19.4 wt%.

[0092] <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 (BAPK) 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 21000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-3 was 21.5 wt %.

[0093] <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 in Production Example 1, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride (BPADA) was used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA. The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 29,000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-4 was 15.0 wt %.

[0094] <Production Example 5> (Synthesis of polyimide precursor (polymer A-5)) Polymer A-5 was obtained by carrying out a reaction in the same manner as in Production Example 1, except that in Production Example 2, 260.2 g of BPADA was used instead of 155.1 g of ODPA and 169.9 g of BAPK 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. The imide group concentration per repeating unit of the polyimide obtained from polymer A-5 was 16.3 wt %.

[0095] <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 BPADA 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.The imide group concentration per repeating unit of the polyimide obtained from polymer A-6 was 17.0 wt%.

[0096] <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 in Production Example 1, 73.6 g of diphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA) and 130.1 g of BPADA were used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 24,000.The imide group concentration per repeating unit of the polyimide obtained from polymer A-7 was 17.1 wt%.

[0097] <Production Example 8> (Synthesis of polyimide precursor (polymer A-8)) Polymer A-8 was obtained by carrying out a 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. The imide group concentration per repeating unit of the polyimide obtained from polymer A-8 was 18.7 wt %.

[0098] <Production Example 9> (Synthesis of polyimide precursor (polymer A-9)) Polymer A-9 was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of ODA. The weight average molecular weight (Mw) of this polymer A-9 was measured and found to be 24,000.The imide group concentration per repeating unit of the polyimide obtained from polymer A-9 was 26.8 wt%.

[0099] <Production Example 10> (Synthesis of polyimide precursor (polymer A-10)) Polymer A-10 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 (BPADA) was used instead of 155.1 g of ODPA and 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 175.9 g of BAPP. The weight average molecular weight (Mw) of this polymer A-10 was measured and found to be 23,000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-10 was 19.1 wt %.

[0100] <Production Example 11> (Synthesis of Polyimide Precursor (Polymer A-11)) 260.2 g of BPADA was placed in a 2-liter separable flask, and 400 ml of γ-butyrolactone was added under a nitrogen atmosphere. m-TB was added with stirring at room temperature to obtain a polyamic acid solution. The mixture was then stirred at 185°C for 4 hours, and after confirming that the theoretical amount of water had been removed, the mixture was cooled to room temperature to obtain polymer A-11. The weight average molecular weight (Mw) of this polymer A-11 was measured and found to be 22,000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-11 was 19.1 wt %.

[0101] <Production Example 12> (Synthesis of Polyimide Precursor (Polymer A-12)) 155.1 g of ODPA was placed in a 2-liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added thereto, and 79.1 g of pyridine was added thereto with stirring at room temperature to obtain a reaction mixture. The reaction mixture was then cooled to -10°C, and 124.4 g of SOCl2 was added over 60 minutes while maintaining the temperature at -10°C. A suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 ml of γ-butyrolactone was then added over 60 minutes with stirring. After stirring for another 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, after which 400 ml of γ-butyrolactone was added. The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a crude polymer precipitate. The resulting crude polymer was dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was purified using a mixture of an anion exchange resin ("Amberlyst TM15" manufactured by Organo Corporation) and a cation exchange resin ("IRA96SB" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuum to obtain powdery polymer A-12. The weight average molecular weight (Mw) of this polymer A-12 was measured and found to be 9000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-12 was 27.4 wt %.

[0102] <Production Example 13> (Synthesis of polyimide precursor (polymer A-13)) Polymer A-13 was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of ODA in Production Example 12. The weight average molecular weight (Mw) of this polymer A-13 was measured and found to be 8000. The imide group concentration per repeating unit of the polyimide obtained from polymer A-13 was 26.8 wt %.

[0103] [Production of Photosensitive Resin Composition] The following compounds were used in the examples and comparative examples. Photoinitiator B-1: TR-PBG-304 (manufactured by Changzhou Strong Electronics Co., Ltd.) Photoinitiator B-2: TR-PBG-305 (manufactured by Changzhou Strong Electronics Co., Ltd.) Photoinitiator B-3: TR-PBG-3057 (manufactured by Changzhou Strong Electronics Co., Ltd.) Organic Compound C-1: Titanium di(n-butoxide) (bis-2,4-pentanedionate) Organic compound C-2: Titanium diisopropoxide bis(ethylacetoacetate) Solvent D-1: γ-butyrolactone (GBL) Solvent D-2: Dimethyl sulfoxide (DMSO)

[0104] Example 1 A negative-tone photosensitive resin composition was prepared using polyimide precursor A-2 by the following method, and the prepared composition was evaluated. (A) 100 g of A-2 as a polyimide precursor, (B) 5 g of B-1 as a photopolymerization initiator, and (D) 100 g of GBL were dissolved. The viscosity of the resulting solution was adjusted to approximately 40 poise by further adding a small amount of GBL. The composition was then left to stand in an incubator IN601 (manufactured by Yamato Scientific Co., Ltd.) at 40°C for 48 hours for aging, yielding a negative-tone photosensitive resin composition. The composition was evaluated according to the aforementioned method. The results are shown in Table 1-1 below.

[0105] <Example 2> A negative photosensitive resin composition similar to that in Example 1 was prepared, except that the aging conditions were changed to 40° C. for 144 hours, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1-1 below.

[0106] Example 3 A negative photosensitive resin composition similar to that in Example 1 was prepared, except that 1 g of C-1 was added as the (C) organic compound and the aging conditions were changed to 23°C for 48 hours, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1-1 below.

[0107] <Examples 4 to 21 and Comparative Examples 1 to 12> Negative photosensitive resin compositions similar to those in Examples 1 to 3 were prepared using the blending ratios shown in Tables 1 and 2 below, and aging was performed, except that they were evaluated in the same manner as in Example 1. In the tables, "-" for the aging temperature and aging time indicates that aging was not performed. The results are shown in Tables 1 and 2 below.

[0108] [Table 1]

[0109] [Table 2]

[0110] As shown in Tables 1 and 2, the imidization rates of the photosensitive resin compositions of Examples 1 to 21 were higher than those of Comparative Examples 1 to 7, 11, and 12. Comparative Examples 8 and 9 showed high absorbance values, and the resolution was "unacceptable." Comparative Example 8 had an imidization rate of 52.6%, exceeding 50%. Comparative Example 10 gelled, making it impossible to carry out evaluation. [Industrial Applicability]

[0111] The photosensitive resin composition of the present invention can be used to obtain a cured film having high resolution and a low dielectric loss tangent even in a thick film. Therefore, the photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) a compound represented by the following general formula (1): 【Chemistry 1】 {In the formula, X 1 is a tetravalent organic group having 6 to 40 carbon atoms, and Y 1 is a divalent organic group having 6 to 40 carbon atoms, and n 1 is an integer from 2 to 150, and 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 2】 (In the formula, 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 of 2 to 10. A polyimide precursor represented by the formula: 100 parts by mass; (B) photosensitizer: 0.5 to 10 parts by mass; and (D) Solvent: 100 to 300 parts by mass; A photosensitive resin composition comprising: a photosensitive resin layer before exposure obtained by removing the solvent from the photosensitive resin composition; and a peak at 1380 cm in an infrared absorption spectrum measured by an ATR (Attenuated Total Reflection) method. -1 The peak intensity near 1500 cm -1 an imidization rate b, which is a value obtained by dividing the imidization index of the photosensitive resin layer, obtained by dividing the intensity of the peak near the peak, by the imidization index of a cured polyimide film obtained by heating and curing the photosensitive resin composition at 350°C, is 15% to 50%, and an imide group concentration a, which is the proportion of imide groups to the molecular weight of a repeating unit containing a structure derived from tetracarboxylic acid and diamine, in the polyimide of the cured polyimide film, is 12 wt% to 30 wt%, and the imide group concentration a and the imide rate b satisfy the following formula (1): 0.10 ≦ 0.01a × (1-0.01b) ≦ 0.17 ... (1) A photosensitive resin composition that satisfies the above requirements.

2. 2. The photosensitive resin composition according to claim 1, wherein the polyimide of the cured polyimide film has an imide group concentration a, which is the ratio of imide groups to the molecular weight of a repeating unit containing a structure derived from tetracarboxylic acid and diamine, of 12 wt % to 24 wt %.

3. 3. The photosensitive resin composition according to claim 1, wherein the polyimide cured film obtained by heating and curing at 350°C has an imidization index of 0.10 to 0.

54.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin layer obtained by applying the photosensitive resin composition to a quartz glass and heating it at 110°C for 3 minutes has an absorbance at 365 nm per 1 µm of 0.02 to 0.

09.

5. Y in the general formula (1) 1 is expressed by the following formula: 【Transformation 3】 In the formula, each Rz is independently a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a is an integer of 0 to 4, A is an oxygen atom or a sulfur atom, and B is a group represented by the following formula: 【Chemistry 4】 The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound is one of the compounds represented by the formula (I):

6. The Y 1 is expressed by the following formula: 【Transformation 5】 or 【Transformation 6】 or 【Transformation 7】 The photosensitive resin composition according to claim 5 , wherein the photosensitive resin composition is represented by the formula:

7. X in the general formula (1) 1 is expressed by the following formula: 【Transformation 8】 In the formula, each Ry is independently a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a is an integer of 0 to 4, C is an oxygen atom or a sulfur atom, and D is a group represented by the following formula: 【Chemistry 9】 The photosensitive resin composition according to any one of claims 1 to 6, wherein the compound is one of the compounds represented by the formula (I):

8. The X 1 is expressed by the following formula: 【Chemistry 10】 or 【Chemistry 11】 The photosensitive resin composition according to claim 7, wherein the photosensitive resin composition is represented by the formula:

9. The photosensitive resin composition is negative-type and contains 50 to 85 parts by mass of (A) a polyimide precursor, 0.5 to 10 parts by mass of (B) a photosensitizer, and 100 to 300 parts by mass of (D) a solvent, and contains 15% by mass to 50% by mass of the polyimide precursor, and the polyimide precursor is represented by the following general formula (11): 【Chemistry 12】 {In the formula, X 1 is a tetravalent organic group having 6 to 40 carbon atoms, and Y 1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.}.

10. The photosensitive resin composition is negative-type and contains 50 to 85 parts by mass of (A) a polyimide precursor, 0.5 to 10 parts by mass of (B) a photosensitizer, and 100 to 300 parts by mass of (D) a solvent, and contains 15% by mass to 50% by mass of the polyimide precursor, and the polyimide precursor is a compound represented by the general formula (1) and a compound represented by the following general formula (11): 【Chemistry 13】 {In the formula, X 1 is a tetravalent organic group having 6 to 40 carbon atoms, and Y 1 is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150.

11. (C) at least one organic compound selected from an organic titanium compound or an organic zirconium compound: 0.01 to 5 parts by mass; The photosensitive resin composition according to any one of claims 1 to 10, further comprising:

12. The photosensitive resin composition according to claim 11, wherein the organic compound (C) is an organic titanium compound.

13. 13. The photosensitive resin composition according to claim 11, wherein the organic titanium compound is at least one compound selected from the group consisting of tetraalkoxytitanium compounds, titanium chelate compounds, titanium acylate compounds, and titanocene compounds.

14. 14. The photosensitive resin composition according to claim 13, wherein the organotitanium compound is a titanium chelate having two or more alkoxy groups or a tetraalkoxytitanium.

15. The photosensitive resin composition according to any one of claims 1 to 14, which is used for forming an interlayer insulating film for a rewiring layer.

16. (E) Monomer: 0.5 to 15 parts by mass; The photosensitive resin composition according to any one of claims 1 to 15, further comprising:

17. 17. The photosensitive resin composition according to claim 16, wherein the monomer (E) contains at least one group selected from the group consisting of a hydroxy group and an amino group.

18. The following steps: a step of mixing the (A) polyimide precursor, the (B) photosensitizer, and the (D) solvent; and a step of aging the obtained mixture at 23°C to 50°C for 24 hours to 360 hours to adjust the imidization rate to 15% to 50%; The method for producing the photosensitive resin composition according to any one of claims 1 to 17, comprising:

19. The following steps (1) to (5): (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 16 onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer; (3) a step of exposing the photosensitive resin layer after heating and drying; (4) developing the exposed photosensitive resin layer; and (5) a step of heat-treating the developed photosensitive resin layer to form a cured polyimide film; A method for producing a cured polyimide film, comprising:

20. The method for producing a cured polyimide film according to claim 19, wherein the cured polyimide film has a dielectric loss tangent of 0.0021 to 0.007 when measured at 10 GHz by a perturbation split cylinder resonator method.

21. The method for producing a cured polyimide film according to claim 19 or 20, wherein the cured polyimide film has a dielectric loss tangent of 0.0021 to 0.008 when measured at 28 GHz by a perturbation split cylinder resonator method.

22. The method for producing a polyimide cured film according to any one of claims 19 to 21, wherein the polyimide cured film has a dielectric loss tangent of 0.0021 to 0.008 when measured at 40 GHz by a perturbation split cylinder resonator method.

23. The method for producing a polyimide cured film according to any one of claims 19 to 22, wherein the polyimide cured film has a dielectric loss tangent of 0.0021 to 0.009 when measured at 60 GHz by a perturbation split cylinder resonator method.

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