TWI880030B - Photosensitive resin composition, method for producing photosensitive resin composition, and method for producing polyimide cured film - Google Patents

Abstract

The subject of the present invention is to provide a photosensitive resin composition that exhibits low dielectric loss tangent, excellent storage stability, and is capable of forming a hardened concave-convex pattern with high resolution.

The photosensitive resin composition of the present invention comprises (A) the following general formula (1):

(B) _a photosensitive agent: 0.5 to 10 parts by weight; and (D) a solvent: 100 to 300 parts by weight. The peak intensity of _the infrared absorption spectrum of _the photosensitive resin layer before exposure obtained by removing _the solvent from _the photosensitive resin composition is divided by the peak intensity of 1500 cm ^- 1. The value obtained by dividing the imidization index of the photosensitive resin layer obtained by the peak intensity near ^-1 by the imidization index of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, that is, the imidization rate is 15%~50%, and in the polyimide of the polyimide cured film, the ratio of the imide group to each repeating unit, that is, the imide group concentration is 12wt%~30wt%.

Description

Photosensitive resin composition, method for producing photosensitive resin composition, and method for producing polyimide cured film

The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a negative photosensitive resin composition that exhibits low dielectric loss tangent, excellent storage stability, and is capable of forming a hardened concave-convex pattern with high resolution, a preparation method thereof, and a method for preparing a polyimide hardened film using the negative photosensitive resin composition.

Previously, insulating materials for electronic parts and passivation films, surface protection films, and interlayer insulating films for semiconductor devices used polyimide resins with excellent heat resistance, electrical properties, and mechanical properties. Among the polyimide resins, the photosensitive polyimide precursor composition provides a form that can easily form a heat-resistant hardened concave-convex pattern film by coating, exposing, developing, and curing-based thermal imidization treatment of the composition. This photosensitive polyimide precursor composition has the characteristic of greatly reducing the number of steps compared to previous non-photosensitive polyimide materials.

Semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards in various ways according to their purpose. Previously, components were usually manufactured by wire bonding, which connects the external terminals (pads) of the components to the lead frame with relatively fine metal wires. However, recently, from the perspective of high-speed transmission and thinner package height, a semiconductor chip mounting technology called fan-out wafer level packaging (FOWLP) has been proposed. The so-called FOWLP is a mounting technology that manufactures single chips by dicing the wafer that has completed the previous step, reassembles the single chips on a support, seals them with a mold resin, and forms a redistribution layer after peeling off the support.

In recent years, it has become imperative to develop packages for the fifth generation mobile communication system (5G), which is a new communication standard. Unlike the previous 4G technology, 5G uses the millimeter wave (10Gz~80GHz) frequency band to achieve high speed and large capacity/low signal latency/simultaneous connection of multiple terminals that did not exist in previous communications. The millimeter frequency band has a greater impact on transmission loss in the signal wiring of the printed wiring board, and there are concerns about heat generation or transmission delay. Therefore, in order to reduce transmission loss, the front-end module (FEM) that performs radio wave transmission and reception is integrated with the antenna to develop an antenna package (AiP) (for example, refer to the following patent document 1). AiP has shorter wiring length, so it can suppress the transmission loss that increases proportionally with the wiring length.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] U.S. Patent Application Publication No. 2016/0104940

On the other hand, there is a limit to the suppression of transmission loss in packaging design, and improvements in materials are also expected. When the dielectric constant or dielectric loss tangent (tanδ) of the insulating material used to form the wiring is higher, the dielectric loss increases, and the total transmission loss increases. Although polyimide has excellent insulation performance or film properties, since the imide group itself is a polar functional group, and the photosensitive polyimide precursor composition contains a large amount of polar compounds such as photopolymerization initiators or crosslinking agents, the dielectric constant or dielectric loss tangent is high, and the dielectric properties need to be reduced.

In view of the current state of the art, the problem to be solved by the present invention is to provide a negative photosensitive resin composition that exhibits low dielectric loss tangent, excellent storage stability, and is capable of forming a hardened concave-convex pattern with high resolution, a preparation method thereof, a polyimide hardened film using the photosensitive resin composition, a method for manufacturing a hardened concave-convex pattern, and a semiconductor device having the hardened concave-convex pattern.

The inventors of the present invention unexpectedly discovered that the above-mentioned problem can be solved by adjusting the properties of the photosensitive resin composition containing a polyimide precursor, thereby completing the present invention.

That is, the present invention is as follows.

[1] A photosensitive resin composition comprising:

(A) 100 parts by weight of a polyimide precursor represented by the following general formula (1);

{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 of 2 to 150, _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R1 and _R2 is a group represented by the following general formula (2):

(wherein, R ₃ , R ₄ and R ₅ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10)}

(B) Photosensitizer: 0.5~10 parts by mass; and

(D) Solvent: 100-300 parts by weight; the peak intensity of the infrared absorption spectrum of the photosensitive resin layer before exposure obtained by ATR (Attenuated Total Reflection) method at around 1380 cm ^-1 is divided by 1500 cm-1. The value obtained by dividing the imidization index of the photosensitive resin layer obtained by the peak intensity near ^-1 by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350°C, that is, the imidization rate b is 15%~50%, and in the polyimide of the polyimide cured film, the ratio of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic acid and diamine, that is, the imide group concentration a is 12wt%~30wt%.

[2] A photosensitive resin composition as described in [1] above, wherein the above-mentioned imide group concentration a and imidization rate b satisfy the following formula (1): 0.10≦a×(1-b)≦0.17 (1).

[3] A photosensitive resin composition as described in [1] or [2] above, wherein in the polyimide of the polyimide cured film, the ratio of the imide group to the molecular weight of the repeating unit comprising a structure derived from tetracarboxylic acid and diamine, i.e., the imide group concentration a, is 12wt% to 24wt%.

[4] The photosensitive resin composition of 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] A photosensitive resin composition as described in any one of [1] to [4] above, wherein the absorbance of the photosensitive resin layer obtained by coating the photosensitive resin composition on quartz glass and heating it at 110°C for 3 minutes at 365nm is 0.02-0.09 per 1μm.

[6] The photosensitive resin composition of any one of [1] to [5] above, wherein _Y1 in the general formula (1) is represented by the following formula:

}。 {wherein, 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 one of the following formulae:

}.

[7] The photosensitive resin composition of [6] above, wherein _Y1 is represented by the following formula:

or

or

[8] The photosensitive resin composition of any one of [1] to [7] above, wherein _X1 in the general formula (1) is represented by the following formula:

}。 {wherein, 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 one of the following formulae:

}.

[9] The photosensitive resin composition of [8], wherein _X1 is represented by the following formula:

or

[10] A photosensitive resin composition as described in any one of [1] to [9] above, wherein the photosensitive resin composition is a negative type and contains (A) 50-85 parts by weight of a polyimide precursor, (B) 0.5-10 parts by weight of a photosensitive agent, and (D) 100-300 parts by weight of a solvent, and contains 15% by weight to 50% by weight of the polyimide precursor, and the polyimide precursor is a polyimide precursor represented by the general formula (1) having a structure represented by the following general formula (11) in the molecule:

{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] A photosensitive resin composition as described in any one of [1] to [9] above, wherein the photosensitive resin composition is a negative type and contains (A) 50-85 parts by weight of a polyimide precursor, (B) 0.5-10 parts by weight of a photosensitive agent, and (D) 100-300 parts by weight of a solvent, and contains 15% by weight to 50% by weight of the polyimide precursor, and the polyimide precursor is a blend of the polyimide precursor represented by the general formula (1) and a polyimide having a structure represented by the following general formula (11):

{wherein, X ¹ is a tetravalent organic group having 6 to 40 carbon atoms, Y ¹ is a divalent organic group having 6 to 40 carbon atoms, and m is an integer of 2 to 150}.

[12] A photosensitive resin composition as described in any one of [1] to [11] above, further comprising (C) 0.01 to 5 parts by weight of at least one organic compound selected from an organic titanium compound or an organic zirconium compound.

[13] The photosensitive resin composition of [12] above, wherein the organic compound (C) is an organic titanium compound.

[14] A photosensitive resin composition as described in [12] or [13] above, wherein the organic titanium compound is at least one compound selected from the group consisting of tetraalkoxy titanium compounds, titanium chelate compounds, titanium acylate compounds, and titanocene compounds.

[15] A photosensitive resin composition as described in [14] above, wherein the organic titanium compound is a titanium chelate or a titanium tetraalkoxide having two or more alkoxy groups.

[16] A photosensitive resin composition as described in any one of [1] to [15] above, which is used to form an interlayer insulating film for a redistribution layer.

[17] A photosensitive resin composition as described in any one of [1] to [16] above, further comprising (E) monomer: 0.5 to 15 parts by weight.

[18] A photosensitive resin composition as described in [17] above, wherein the (E) monomer contains at least one group selected from the group consisting of a hydroxyl group and an amino group.

[19] A method for preparing a photosensitive resin composition as described in any one of [1] to [18] above, comprising the following steps: a step of mixing the above (A) polyimide precursor, the above (B) photosensitive agent, and the above (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%.

[20] A method for producing a polyimide cured film, comprising the following steps (1) to (5): (1) coating a photosensitive resin composition as described in any one of [1] to [17] on a substrate to form a photosensitive resin layer on the substrate; (2) heating and drying the obtained photosensitive resin layer; (3) exposing the heated and dried photosensitive resin layer; (4) developing the exposed photosensitive resin layer; and (5) heating the developed photosensitive resin layer to form a polyimide cured film.

[21] A method for manufacturing a polyimide cured film as described in [20] above, wherein the dielectric loss tangent of the polyimide cured film measured at 10 GHz using a perturbation split cylindrical resonator method is 0.0021 to 0.007.

[22] A method for manufacturing a polyimide cured film as described in [20] or [21] above, wherein the dielectric loss tangent of the polyimide cured film is 0.0021 to 0.008 when measured at 28 GHz using a perturbation split cylindrical resonator method.

[23] A method for producing a polyimide cured film as described in any one of [20] to [22] above, wherein the dielectric loss tangent of the polyimide cured film measured at 40 GHz using a perturbation split cylindrical resonator method is 0.0021 to 0.008.

[24] A method for producing a polyimide cured film as described in any one of [20] to [23] above, wherein the dielectric loss tangent of the polyimide cured film measured at 60 GHz using a perturbation split cylindrical resonator method is 0.0021 to 0.009.

[25] A method for producing a polyimide cured film, which is a method for producing a polyimide cured film using the following photosensitive resin composition, wherein the photosensitive resin composition comprises:

(A) 100 parts by weight of a polyimide precursor represented by the following general formula (1);

{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 of 2 to 150, _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R1 and _R2 is a group represented by the following general formula (2):

(wherein, R ₃ , R ₄ and R ₅ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10)}

(B) Photosensitizer: 0.5~10 parts by mass; and

(D) solvent: 100-300 parts by weight; the above-mentioned manufacturing method comprises the following steps (1)-(5): (1) coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate; (2) heating and drying the obtained photosensitive resin layer to remove the solvent; (3) treating the photosensitive resin layer after the solvent is removed. (4) developing the exposed photosensitive resin layer; and (5) heating the developed photosensitive resin layer to form a polyimide cured film. The imidization rate of the photosensitive resin layer before exposure obtained by heating and drying and then removing the solvent in step (2) is 15-50%.

By using the photosensitive resin composition of the present invention, a cured resin film with excellent dielectric loss tangent can be produced while maintaining the resolution of the concave-convex pattern of the thick film. In one embodiment, by increasing the imidization rate of the photosensitive resin layer obtained from the photosensitive resin composition to a specific range, the polar compound derived from the side chain of the polyimide precursor is easily removed during the heating step, which can reduce the dielectric loss tangent of the obtained cured film and reduce the frequency dependence. In addition, by adjusting the absorbance of the photosensitive resin layer obtained from the photosensitive resin composition to a specific range, the resolution of the concave-convex pattern of the thick film can be maintained.

The following is a detailed description of the method for implementing the present invention (hereinafter referred to as "implementation method"). Furthermore, the present invention is not limited to the following implementation method, and can be implemented after various changes within the scope of its main purpose. In this specification, when there are multiple structures represented by the same symbol in the general formula in the molecule, unless otherwise specified, they are independently selected and can be the same or different. In addition, structures represented by common symbols in different general formulas are also independently selected and can be the same or different unless otherwise specified.

[Photosensitive resin composition]

The photosensitive resin composition of this embodiment includes (A) a polyimide precursor, (B) a photosensitive agent (photopolymerization initiator), and (D) a solvent, and optionally further includes (C) an organic compound, such as a titanium or zirconium compound, (E) a monomer, and other components.

Below, each component is explained in order.

From the perspective of the physical properties of the polyimide precursor described below (A), the photosensitive resin composition is preferably negative.

The photosensitive resin composition that can be preferably used in the present invention is one whose absorbance at 365nm (i-ray) is 0.02~0.09 per 1μm.

The i-ray absorbance of a film with a thickness of 1μm can be measured by pre-baking a coating formed by forming a photosensitive polyimide precursor alone on quartz glass, and then using a conventional spectrophotometer. When the thickness of the formed film is not 1μm, the absorbance obtained for the film is converted to a thickness of 1μm according to the Lambert-Beer law, and the i-ray absorbance of a film with a thickness of 1μm can be obtained.

The i-ray absorbance is preferably 0.04 or more, and from the perspective of suppressing reflected light, it is more preferably 0.05 or more. The so-called reflected light is light that is not absorbed in the film and travels to the bottom of the film and is reflected by the substrate, which will cause poor patterning. If the i-ray absorbance is 0.09 or less, the light reaches the bottom of the photosensitive resin layer, which can ensure the difference in solubility between the soluble part and the insoluble part.

[(A) Polyimide precursor]

In the present embodiment, (A) the polyimide precursor is a resin component contained in the photosensitive resin composition and is a polyimide having a structural unit represented by the following general formula (1):

{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 of 2 to 150, _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R1 and _R2 is a group represented by the following general formula (2):

(wherein, R ₃ , R ₄ and R ₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10)}. Furthermore, R ₁ and R ₂ in the general formula (1) are also referred to as the side chain or side chain structure of the polyimide precursor.

From the perspective of the photosensitivity and mechanical properties of the photosensitive resin composition, n1 in the above general formula (1) is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

In the above general formula (1), in terms of both heat resistance and photosensitivity, the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group or alicyclic aliphatic group in which _-COOR1 and _-COOR2 are adjacent to -CONH-. As the tetravalent organic group represented by _X1 , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, a group having a structure represented by the following general formula (20):

[Chemistry 19]

{In formula (20), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, and a C1-C10 fluorine-containing alkyl group, 1 is an integer of 0-2, m is an integer of 0-3, and n is an integer of 0-4}, but is not limited thereto. In addition, the structure of _X1 may be one type or a combination of two or more types. In terms of both heat resistance and photosensitivity, the _X1 group having the structure represented by the above formula (20) is particularly preferred.

In the above general formula (1), in terms of both heat resistance and photosensitivity, the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms, for example, the structure represented by the following general formula (21):

{In formula (21), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, and a C1-C10 fluorine-containing alkyl group, m is an integer of 0-3, and n is an integer of 0-4}, but is not limited thereto. In addition, the structure of _Y1 may be one type or a combination of two or more types. In terms of both heat resistance and photosensitivity, a _Y1 group having a structure represented by the above formula (21) is particularly preferred.

As the _Y1 group, from the viewpoint of low dielectric loss tangent, low dielectric constant, and lithographic properties, among the structures represented by the above formula (21), the structure represented by the following formula is particularly preferred:

{In the formula, R6 is a univalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, and a C1-C10 fluorine-containing alkyl group, m is an integer of 0-3, and n is an integer of 0-4}.

In the general formula (2), _R3 is preferably a hydrogen atom or a methyl group. From the viewpoint of photosensitivity, _R4 and _R5 are preferably hydrogen atoms. From the viewpoint of photosensitivity, _m1 is an integer of 2 to 10, preferably an integer of 2 to 4.

In this specification, the term "imide group concentration" refers to the ratio of the mass of imide groups in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition of the present embodiment, relative to the molecular weight of the repeating units containing the structure derived from tetracarboxylic acid and diamine.

Furthermore, in this specification, the term "polyimide precursor" includes a portion of the polyimide precursor that is undergoing imidization.

In this embodiment, the obtained polyimide cured film has an amide group concentration of 12wt% to 30wt%, preferably 12wt% to 24wt%. If the amide group concentration is 12wt% or more, the adhesion between the molding resin and the cured concave-convex pattern tends to be good. The amide group concentration is preferably 12.5wt% or more, and more preferably 13.5wt% or more. On the other hand, by making the amide group concentration below 30wt%, the dielectric loss tangent of the obtained polyimide cured film tends to be good. The amide group concentration is more preferably 23.0wt% or less, and further preferably 21.0wt% or less.

The imide group concentration in each repeating unit of polyimide is the molecular weight of the tetracarboxylic acid and diamine used in the adjustment of the polyimide precursor, and is represented by 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}. Furthermore, when two or more tetracarboxylic acids and/or diamines are used, for example, when two tetracarboxylic acids and/or diamines are used for adjustment, it is represented by the following formula (II): 70.02×2/[Mw(A1)×a ₁ +Mw(A2)×a ₂ +Mw(B1)×b ₁ +Mw(B2)×b ₂ ]×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; wherein _a1 , _a2 , _b1 , and _b2 satisfy _a1 + _a2 =1 and _b1 + _b2 =1, respectively}.

When three or more tetracarboxylic acids and/or diamines are used, the same method is used for calculation. When tetracarboxylic dianhydride is used as a raw material, it is calculated after conversion to tetracarboxylic acid.

The peak intensity ratio of 1380 cm ^-1 to 1500 cm ^-1 (imidization index of the cured film) measured by the ATR method for the cured film obtained from the photosensitive resin composition represents the ratio of the imide group (1380 cm ^-1 ) to the aromatic ring (1500 cm ^-1 ) in the cured film. In the present embodiment, X ₁ and Y ₁ in the general formula (1) are preferably selected from structures having an imidization index of 0.10 to 0.54 for the cured film, preferably 0.10 to 0.53 from the viewpoint of low dielectric loss tangent, and more preferably 0.35 to 0.53 from the viewpoint of lithographic properties.

(A) Preparation method of polyimide precursor

The polyimide precursor having a structure represented by the general formula (1) in the present embodiment is obtained, for example, by a method comprising: reacting the tetracarboxylic dianhydride having a 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) is bonded to a hydroxyl group, and optionally (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 then condensing the obtained acid/ester with the diamine having a divalent organic group _Y1 having 6 to 40 carbon atoms.

(Preparation of acid/ester)

In the present embodiment, the tetracarboxylic dianhydride containing a tetravalent organic group _X1 having 6 to 40 carbon atoms may be, for example, pyromellitic dianhydride, diphenyl ether-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'-isopropylidene diphenoxy) acid dianhydride, and the like. These may be used alone or in combination of two or more.

As (b) alcohols having a structure other than the group represented by the above general formula (2), for example, 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, benzyl alcohol, etc.

The content of the organic group of the general formula (2) in the polyimide precursor is preferably 50 mol% or more relative to the total content of _R1 and _R2 in the general formula (1). If the content of the organic group of the general formula (2) exceeds 50 mol%, the desired photosensitivity can be obtained, which is preferred.

The content of the organic group of the general formula (2) in the photosensitive resin composition is preferably 75 mol% or more relative to the total content of _R1 and _R2 in the general formula (1).

The above-mentioned tetracarboxylic dianhydride and the alcohols (a) are dissolved and mixed in a reaction solvent in the presence of an alkaline catalyst such as pyridine, thereby carrying out a half-esterification reaction of the dianhydride to obtain the desired acid/ester. The preferred reaction conditions are stirring at a reaction temperature of 20~50℃ for 4~10 hours.

The reaction solvent is preferably one that dissolves the acid/ester and a polyimide precursor that is a condensation product of the acid/ester and a diamine. Examples of the reaction solvent include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-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, xylene, etc. These can be used alone or in combination of two or more as needed.

(Preparation of polyimide precursor)

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

Examples of the 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 sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3 '-Diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]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-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl] )phenyl}propane, bis{4-(4-aminophenoxy)phenyl}ketone, and those in which a part of the hydrogen atoms on the benzene ring is substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamines are not limited to these.

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

After the polycondensation reaction is completed, the water-absorbing byproducts of the dehydration condensation agent coexisting in the reaction solution can be filtered and separated as needed, and then a poor solvent such as water, aliphatic lower alcohol or a mixture thereof can be added to the reaction solution to precipitate the polymer components. Furthermore, the polymer can be purified by repeatedly performing the above-mentioned re-dissolution and re-precipitation operations. Next, the polymer can be vacuum dried to isolate the polyimide precursor. In order to improve the degree of purification, the polymer solution can also be passed through a column filled with an anion and/or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

When the molecular weight of the polyimide precursor (A) is measured as a weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC), it is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000. If the weight average molecular weight is 8,000 or more, the mechanical properties are good, so it is preferred. On the other hand, if it is 150,000 or less, the dispersibility in the developer and the resolution performance of the concave-convex pattern are good, so it is preferred. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained based on a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko Co., Ltd.

The photosensitive resin composition using the (A) polyimide precursor is imidized by a compound contained in the photosensitive resin composition, and/or in the manufacturing step of the photosensitive resin composition, a part of the (A) polyimide precursor is imidized in the resin composition.

In this embodiment, when measured by the ATR method, from the perspective of low dielectric loss tangent, absorbance, and resolution, the imidization rate of the (A) polyimide precursor in the resin composition is 15% to 50%, preferably 15% to 40%. The absorbance of the polyimide precursor is related to the imidization rate, and if the imidization rate increases, the absorbance will also increase. In this specification, the term "imidization rate" is calculated as a value obtained by dividing the peak intensity of 1380 cm ^-1 in the infrared spectrum by the peak intensity of 1500 cm ^-1 as the "imidization index of the photosensitive resin layer" by the "imidization index of the cured film" obtained by curing the photosensitive resin composition at 350°C.

If the polyimide precursor is imidized, the side chains of R1 and R2 in the general formula (1) are detached and dispersed in the resin composition along with the ring-closing reaction. In the present embodiment, since a portion of the polyimide precursor in the photosensitive resin composition is imidized, the side chains are already dispersed in the resin composition before heat curing, so the concentration of methacrylate in the resin composition does not change and the lithography can be maintained. On the other hand, the methacrylate is easily volatilized by the heat of the heat curing step, so the residual amount of polar compounds in the cured film can be reduced.

From the perspective of low dielectric loss tangent and absorbance, it is preferred that the imide group concentration a and the imide rate b satisfy the following formula (1): 0.10≦a×(1-b)≦0.17 (1).

Without theoretical constraints, by making a×(1-b) in the range of 0.1~0.17, the residual amount of the polyimide precursor side chain in the polyimide cured film is reduced to achieve low dielectric loss tangent. In addition, the absorbance that increases with the progress of imidization can be kept below a certain value.

[(B) Photosensitizer]

、2-甲基9-氧硫

、2-異丙基9-氧硫

、二乙基9-氧硫

等9-氧硫

衍生物；苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物；安息香、安息香甲醚等安息香衍生物；1-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟等肟類；N-苯基甘胺酸等N-芳基甘胺酸類；過氯化苯甲醯等過氧化物類；芳香族聯咪唑類、二茂鈦類、α-(正辛磺醯氧基亞胺基)-4-甲氧基苄基氰化物等光酸產生劑類等；但並不限定於該等。於上述光聚合起始劑之中，尤其是就感光度之方面而言，更佳為肟類。 The photosensitive resin composition of this embodiment contains a photosensitive agent. In one embodiment, the photosensitive agent can also be a photopolymerization initiator. The photopolymerization initiator promotes the hardening of the concave-convex pattern based on light irradiation, so it is preferred. As the photopolymerization initiator, it is preferably a photo-free radical polymerization initiator, and preferably exemplified are: benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; 9-oxysulfuron

, 2-methyl 9-oxosulfur

, 2-isopropyl 9-oxysulfide

, diethyl 9-sulfoxide

9-Oxosulfur

derivatives; benzoyl derivatives such as benzoyl dimethyl ketal and benzoyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2- Oxime such as (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime; N-arylglycine such as N-phenylglycine; peroxide such as perchlorinated benzoyl; photoacid generator such as aromatic biimidazoles, titanocene, α-(n-octylsulfonyloxyimino)-4-methoxybenzyl cyanide, etc., but not limited to them. Among the above-mentioned photopolymerization initiators, oximes are more preferred in terms of sensitivity.

The amount of the photopolymerization initiator is 0.5 to 10 parts by mass, preferably 1 to 8 parts by mass, relative to 100 parts by mass of the polyimide precursor (A). From the perspective of photosensitivity or patterning, the amount is 0.5 parts by mass or more, and from the perspective of the physical properties of the photosensitive resin layer after the photosensitive resin composition is cured, it is preferably 10 parts by mass or less.

[(C) Organic compounds]

In this embodiment, the photosensitive resin composition may also contain (C) an organic compound. The (C) organic compound preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. Preferably, the organic group contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. By containing the above-mentioned 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.

As the organic titanium or zirconium compounds that can be used, for example, there are those in which an organic group is bonded to a titanium atom or a zirconium atom via a covalent bond or an ionic bond.

Specific examples of organic titanium or zirconium compounds are shown in the following I) to VII): As I) chelate compounds, compounds having two or more alkoxy groups are more preferred in terms of the storage stability of the photosensitive resin composition and the acquisition of good patterns. Specific examples of chelate compounds include: titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-pentanedioate)di-n-butanol, titanium bis(2,4-pentanedioate)diisopropoxide, titanium bis(tetramethylpimelate)diisopropoxide, titanium diisopropoxidedi(ethyl acetylacetate), and compounds in which the titanium atoms of these compounds are replaced by zirconium atoms; but they are not limited to these.

Examples of II) tetraalkoxy compounds include: titanium tetra-n-butoxide, titanium tetraethanol, titanium tetra(2-ethylhexyl)ol, titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethylol, titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra-n-nonoxide, titanium tetra-n-propoxide, titanium tetrastearylol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], and compounds in which the titanium atoms of these compounds are replaced by zirconium atoms; however, the compounds are not limited to these.

Examples of the titanium or zirconium cyclopentadienyl compound (III) include titanium pentamethylcyclopentadienyltrimethoxide, titanium bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds wherein the titanium atom of these compounds is substituted with a zirconium atom; however, the present invention is not limited to these.

Examples of IV) monoalkoxy compounds include: titanium tri(dioctylsulfonate)isopropoxide, titanium tri(dodecylbenzenesulfonate)isopropoxide, and compounds in which the titanium atom is replaced by a zirconium atom; but the compounds are not limited to these.

Examples of V) titanium or zirconium oxide compounds include: bis(glutaric acid)titanium oxide, bis(tetramethylpimelic acid)titanium oxide, phthalocyanine oxidetitanium oxide, and compounds in which the titanium atoms of these compounds are replaced by zirconium atoms; but the compounds are not limited to these.

Examples of titanium tetraacetylpyruvate or zirconium tetraacetylpyruvate compounds (VI) include titanium tetraacetylpyruvate and compounds in which the titanium atom of these compounds is replaced by a zirconium atom; however, the compounds are not limited to these.

As VII) titanium ester coupling agent, for example, tri(dodecylbenzenesulfonyl)titanium isopropyl ester can be cited, but it is not limited to them.

Among the above I) to VII), from the viewpoint of achieving a better dielectric loss tangent, the organic titanium compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanocene compound. Titanium diisopropyl alcohol bis(ethyl acetate), titanium tetra-n-butoxide, and bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

The amount of the organic titanium or zirconium compound to be mixed with 100 parts by mass of the resin (A) is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass. If the amount is 0.01 parts by mass or more, the imidization rate of the resin composition and the dielectric loss tangent of the cured film are good. On the other hand, if it is 10 parts by mass or less, the storage stability is excellent, so it is better.

The photosensitive resin composition of the present embodiment can increase the imidization rate of the polyimide precursor contained in the resin composition by containing the above-mentioned (C) organic compound, and can reduce the dielectric loss tangent of the cured film using the resin composition. Without being bound by theory, it is believed that the reason for increasing the imidization rate of the polyimide precursor is that the metal element contained in the (C) organic compound coordinates to the ester group and/or the carbonyl group derived from the 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 reducing the dielectric loss tangent is believed to be that the ring closing reaction is locally carried out before the heat treatment used for curing the resin composition, so in the following general formula (1):

In the polyimide precursor represented by {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 of 2 to 150, and _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms}, _R1 and/or _R2 are separated from the polymer structure by the ring closure of the polyimide precursor and are easily volatilized in the heating step in the curing film manufacturing step. Furthermore, when _R1 and/or _R2 have a polymerizable functional group, it will remain in the film during the exposure step in the hardened film manufacturing step. Therefore, even if the imidization rate is adjusted, the concentration of the polymerizable functional group in the film will not change, and will not affect the resolution.

[(D) Solvent]

The photosensitive resin composition of this embodiment contains (D) a solvent (also referred to as a solvent). As the solvent, a polar organic solvent is preferably used in terms of solubility in the (A) polyimide precursor. Specifically, the solvent may 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-imidazolidinone, N-cyclohexyl-2-pyrrolidone, 2-octanone, etc.; these may be used alone or in combination of two or more.

In this embodiment, the above-mentioned (D) solvent corresponds to the required coating film thickness and viscosity of the photosensitive resin composition, and is in the range of 100 to 300 parts by mass relative to 100 parts by mass of (A) polyimide precursor.

From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol is preferred. Alcohols that can be preferably used are typically alcohols having an alcoholic hydroxyl group in the molecule but not having an olefinic double bond, and specific examples include: alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol; lactic acid 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-hydroxy isobutyric acid esters; and diols such as ethylene glycol and propylene glycol. Among them, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxy isobutyric acid esters, and ethanol 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.

When the solvent contains an alcohol without an olefinic double bond, the content of the alcohol without an olefinic double bond in the total solvent is preferably 5% to 50% by mass, and more preferably 10% to 30% by mass, based on the mass of the total solvent. If the content of the alcohol without an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good. On the other hand, if it is 50% by mass or less, the solubility of the (A) polyimide precursor becomes good.

[(E) Monomer]

酯或甲基丙烯酸酯、丙烯醯胺、其衍生物、甲基丙烯醯胺、其衍生物、三羥甲基丙烷三丙烯酸酯或甲基丙烯酸酯、甘油之二或三丙烯酸酯或甲基丙烯酸酯、季戊四醇之二、三或四丙烯酸酯或甲基丙烯酸酯、該等化合物之環氧乙烷或環氧丙烷 加成物等化合物。又，該等單體可使用1種，亦可以2種以上之混合物使用。 In this embodiment, in order to improve the resolution of the concavo-convex pattern, the photosensitive resin composition may arbitrarily contain a (E) monomer having a photopolymerizable unsaturated bond. As such a monomer, a (meth)acrylic compound that undergoes a free radical polymerization reaction by a photopolymerization initiator is preferred, and is not particularly limited to the following, and examples thereof include mono- or di-acrylates or methacrylates of ethylene glycol or polyethylene glycol represented by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or di-acrylates or methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates or methacrylates of glycerol, cyclohexane diacrylate or dimethacrylate, diacrylate or dimethacrylate of 1,4-butanediol, diacrylate or dimethacrylate of 1,6-hexanediol, diacrylate or dimethacrylate of neopentyl glycol, mono- or di-acrylate or methacrylate of bisphenol A, benzyltrimethacrylate, isoacrylate,

esters or methacrylates, acrylamide, its derivatives, methacrylamide, its derivatives, trihydroxymethylpropane triacrylate or methacrylate, glycerol di- or triacrylate or methacrylate, pentaerythritol di-, tri- or tetraacrylate or methacrylate, ethylene oxide or propylene oxide adducts of these compounds, etc. These monomers may be used alone or as a mixture of two or more.

If the polyimide precursor contained in the resin composition is ring-closed by aging the resin composition, the side chain molecules will be separated, but the separated side chain molecules can exist as monomers in the resin composition. The monomer preferably has at least one group selected from hydroxyl group and amino group, and more preferably has a structure represented by the following general formula (3):

{In formula (3), Z is at least one group selected from the group consisting of hydroxyl groups and amino groups, R ₇ , R ₈ and R ₉ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10}.

In this embodiment, the amount of the monomer having a photopolymerizable unsaturated bond is 0.5 to 15 parts by mass relative to 100 parts by mass of (A) polyimide precursor.

[Other ingredients]

The photosensitive resin composition of this embodiment may further contain components other than the above-mentioned (A) to (E) components. Examples of other components include: (A) resin components other than polyimide precursors; sensitizers; monomers having photopolymerizable unsaturated bonds; photopolymerization aids; thermal polymerization inhibitors; azole compounds; and hindered phenol compounds, etc.

唑、聚

唑前驅物、酚系樹脂、聚醯胺、環氧樹脂、矽氧烷樹脂、丙烯酸系樹脂等。相對於(A)聚醯亞胺前驅物100質量份，該等樹脂成分之調配量較佳為0.01質量份~20質量份之範圍。 In one embodiment, the photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. Examples of the resin component that may be contained in the photosensitive resin composition include polyimide, poly

Azoles, poly

The amount of the resin components is preferably in the range of 0.01 to 20 parts by weight relative to 100 parts by weight of the (A) polyimide precursor.

唑前驅物來製備正型感光性樹脂組合物之情形時，作為正型感光材，可將具有醌二疊氮基之化合物、例如具有1,2-苯醌二疊氮結構或1,2-萘醌二疊氮結構之化合物等併用。 (A) a polyimide precursor and a polyimide

When a positive-type photosensitive resin composition is prepared by using an azole 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, can be used in combination as a positive-type photosensitive material.

唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯等。該等可單獨或以複數種(例如2~5種)之組合使用。 In one embodiment, in order to improve the sensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of the sensitizer include: michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4, 4'-Bis(diethylamino)chalcone, p-dimethylaminocinnamylene, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethyl Aminocumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-butylbenzimidazole, 1-phenyl-5-butyltetrazole, 2-butylbenzothiazole, 2-(p-dimethylaminostyryl)benzo

azole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminophenylvinyl)styrene, etc. These can be used alone or in combination of plural types (e.g., 2 to 5 types).

Relative to 100 parts by weight of (A) polyimide precursor, the preferred amount of sensitizer is 0.1 to 25 parts by weight.

In one embodiment, in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may arbitrarily contain a bonding aid. Examples of the bonding aid include: γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidyloxypropyl methyl dimethoxysilane, γ-butyl propyl methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidyloxypropyl methyl silane, N-(3-diethoxymethylsilyl)propyl Silane coupling agents such as 3-(triethoxysilyl) succinimide, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, and aluminum-based bonding agents such as tris(ethylacetoacetate)aluminum and tris(acetylacetonate)aluminum. These bonding agents may be used alone or as a mixture of two or more.

Among these bonding aids, silane coupling agents are more preferred in terms of bonding strength. The amount of bonding aid is preferably in the range of 0.5 to 25 parts by weight relative to 100 parts by weight of (A) polyimide precursor.

、N-苯基萘基胺、乙二胺四乙酸、1,2-環己烷二胺四乙酸、二醇醚二胺四乙酸、2,6-二-第三丁基-對甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺丙基胺基)苯酚、N-亞硝基-N-苯基羥基胺銨鹽、N-亞硝基-N(1-萘基)羥基胺銨鹽等。又，該等熱聚合抑制劑可使用1種，亦可以2種以上之混合物使用。 In one embodiment, in order to improve the stability of the viscosity and sensitivity of the photosensitive resin composition, especially when stored in a solution containing a solvent, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butyl o-cyclopentylphenol, phenanthridine,

, 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. In addition, these thermal polymerization inhibitors may be used alone or as a mixture of two or more.

The amount of thermal polymerization inhibitor to be added is preferably in the range of 0.005 to 12 parts by weight relative to 100 parts by weight of (A) polyimide precursor.

For example, when a substrate comprising copper or a copper alloy is used, the photosensitive resin composition may optionally contain an azole compound in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-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, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Moreover, these azole compounds may be used alone or as a mixture of two or more.

The amount of the azole compound to be added is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of sensitivity characteristics. If the amount of the azole compound to be added is 0.1 parts by mass or more relative to 100 parts by mass of the polyimide precursor (A), discoloration of the surface of copper or copper alloy is suppressed when a photosensitive resin composition is formed on copper or copper alloy. On the other hand, if it is 20 parts by mass or less, the sensitivity is excellent, so it is preferred.

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第二丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-(1-乙基丙基)-3-羥基-2,6-二甲基苄基]-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-三乙基甲基-3-羥基-2,6-二甲基苄基]-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(3-羥基-2,6-二甲基-4-苯基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5,6-三甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2,5-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5,6-二乙基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮等；但並不限定於此。該等之中，尤佳為1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮。 In the present embodiment, in order to suppress discoloration on copper, the photosensitive resin composition may include a hindered phenol compound. Examples of the hindered phenol compound include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate isooctyl ester, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl- 6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, etc., but not limited thereto. Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione.

The amount of the hindered phenol compound to be added is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A). From the perspective of photosensitivity characteristics, it is more preferably 0.5 to 10 parts by mass. If the amount of the hindered phenol compound to be added is 0.1 parts by mass or more relative to 100 parts by mass of the polyimide precursor (A), when a photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or a copper alloy can be prevented. On the other hand, if it is less than 20 parts by mass, the photosensitivity is excellent, so it is preferred.

The photosensitive resin composition of the present embodiment can be manufactured by a manufacturing method comprising the following steps: a step of mixing the above-mentioned (A) polyimide precursor, the above-mentioned (B) photosensitive agent, and the above-mentioned (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%.

"Aging" is a step of leaving the photosensitive resin composition at a fixed temperature for a certain period of time. The aging temperature is 23℃~50℃, preferably 30~50℃. The aging time is 24 hours~360 hours, preferably 48 hours~280 hours. The photosensitive resin composition can be defoamed by the aging, and the imidization rate of the (A) polyimide precursor in the photosensitive resin composition can be adjusted to a specific range.

[Polyimide]

The polyimide contained in the hardened concave-convex pattern formed by the polyimide precursor composition preferably has a structure represented by the following general formula (11):

{In the general formula (11), ^X1 and ^Y1 are the same as _X1 and _Y1 in the general formula (1), and m is a positive integer}.

Preferred _X1 and _Y1 in the general formula (1) are also preferred in the polyimide of the general formula (11) for the same reason. The number of repeating units m in the general formula (11) is not particularly limited and can be an integer of 2 to 150.

[Curing film and its manufacturing method]

Another embodiment of the present invention is a method for producing a polyimide cured film, which includes the step of converting the above-mentioned photosensitive resin composition into polyimide.

That is, the method for producing a polyimide cured film of the present embodiment comprises the following steps (1) to (5): (1) coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate; (2) heating and drying the obtained photosensitive resin layer; (3) exposing the heated and dried photosensitive resin layer; (4) developing the exposed photosensitive resin layer; and (5) developing the developed photosensitive resin layer. The present invention further comprises a step of heat-treating the photosensitive resin layer to form a polyimide cured film. In another embodiment of the present invention, a polyimide cured film obtained from the photosensitive resin composition described above and a method for producing the same are provided. The dielectric loss tangent of the cured film is preferably 0.0021 to 0.007 when measured at 10 GHz using a perturbation split cylindrical resonator method, and more preferably 0.0030 to 0.0065. The dielectric loss tangent is preferably 0.0021 to 0.008 when measured at 28 GHz, and more preferably 0.0030 to 0.0075 from the viewpoint of frequency dependence. The dielectric loss tangent when measured at 40 GHz is preferably 0.0021 to 0.008, and from the perspective of frequency dependence, it is more preferably 0.0030 to 0.0075. And the dielectric loss tangent when measured at 60 GHz is preferably 0.0021 to 0.009, and from the perspective of frequency dependence, it is more preferably 0.0030 to 0.0085. Furthermore, the dielectric loss tangent can be measured by the perturbation split cylindrical resonator method shown in the following embodiment.

The photosensitive resin composition used in the method for manufacturing the hardened film preferably comprises 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitive agent, and 100 to 300 parts by mass of a solvent, and more preferably comprises a photo-radical polymerization initiator as a photosensitive agent, and further preferably the photosensitive resin composition is a negative type.

The specific steps in the method for manufacturing the hardened film can be carried out according to steps (1) to (5) of the above-mentioned method for manufacturing the hardened film.

The following describes each step.

[(1) The above-mentioned photosensitive resin composition is applied on a substrate to form a photosensitive resin layer on the substrate]

In this step, the photosensitive resin composition of the present embodiment is applied to the substrate and then dried as needed to form a photosensitive resin layer. As the coating method, a method previously used for coating the photosensitive resin composition can be used, such as a coating method using a rotary coater, a rod coater, a doctor blade coater, a curtain coater, a screen printer, etc., a method of spray coating using a spray coater, etc.

[(2) Heating and drying the obtained photosensitive resin layer]

The coating composed of the photosensitive resin composition can be dried as needed, and as a drying method, air drying, heat drying by an oven or a heating plate, vacuum drying, etc. are used. In addition, the drying of the coating is preferably carried out under conditions that do not produce imidization of the (A) polyimide precursor in the photosensitive resin composition. Specifically, when air drying or heat drying is carried out, the drying can be carried out under conditions of 20°C to 140°C and 1 minute to 1 hour. By the above, a photosensitive resin layer can be formed on the substrate.

[(3) The step of exposing the heated and dried photosensitive resin layer]

In this step, an exposure device such as a contact aligner, a mirror projection exposure machine, a stepper, etc. is used, and an ultraviolet light source is used to expose the photosensitive resin layer that has passed through the above (2) step through a patterned mask or a main mask (reticle) or directly.

After that, in order to improve the sensitivity, etc., post-exposure baking (PEB) and/or pre-development baking can be performed at any temperature and time combination as needed. Regarding the range of baking conditions, the temperature is preferably 40℃~120℃, and the time is preferably 10 seconds~240 seconds, but it is not limited to this range as long as the properties of the negative photosensitive resin composition are not damaged. The imidization rate of the polyimide precursor will not change before and after baking.

[(4) The step of developing the exposed photosensitive resin layer]

In this step, the exposed photosensitive resin layer is developed to form a concave-convex pattern.

In this step, when the photosensitive resin composition is negative, the unexposed part of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from previously known photoresist developing methods, such as a rotary spray method, a liquid coating method, an immersion method accompanied by ultrasonic treatment, etc. In addition, after development, in order to adjust the shape of the concave-convex pattern, post-development baking can be performed at any combination of temperature and time as needed. As a developer used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. As good solvents, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. As poor solvents, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are mixed for use, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more solvents, for example, several solvents, may be used in combination.

[(5) The step of heat-treating the developed photosensitive resin layer to form a polyimide cured film]

In this step, the concave-convex pattern obtained by the above-mentioned development is heated to disperse the photosensitive components, and the (A) polyimide precursor is imidized to convert it into a hardened concave-convex pattern containing polyimide. As a method of heat curing, various methods can be selected, such as a method using a heating plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature program. Heating can be performed at 150°C to 400°C for 30 minutes to 5 hours. As an ambient gas during heat curing, air can be used, and inert gases such as nitrogen and argon can also be used.

[Semiconductor devices]

The photosensitive resin composition of this embodiment can also be used to provide a semiconductor device having a hardened concave-convex pattern obtained by the above-mentioned method for manufacturing a hardened concave-convex pattern. Therefore, a semiconductor device having a substrate as a semiconductor element and a hardened concave-convex pattern of polyimide formed on the substrate by the above-mentioned method for manufacturing a hardened concave-convex pattern can be provided. In addition, another embodiment can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-mentioned method for manufacturing a hardened concave-convex pattern as a part of the steps. The semiconductor device of this embodiment can be manufactured by forming the hardened concave-convex pattern formed by the above-mentioned hardened concave-convex pattern manufacturing method as a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device with a bump structure, etc., and combining it with a known semiconductor device manufacturing method.

[Display device]

The photosensitive resin composition of the present embodiment can also be used to provide a display device having a display element and a cured film disposed on the upper portion of the display element, and the cured film is the above-mentioned cured concave-convex pattern. Here, the cured concave-convex pattern can be directly laminated with the display element or sandwiched by other layers. For example, the cured film can be exemplified as: surface protection films, insulating films, and planarization films of TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-Domain Vertical Alignment) type liquid crystal display devices, and partitions for cathodes of organic EL (Electroluminescence) elements.

In addition to being applicable to the semiconductor devices described above, the photosensitive resin composition of this embodiment can also be used for interlayer insulation of multilayer circuits, covering coatings of flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[Implementation example]

The present invention is described in detail below by way of examples, but the present invention is not limited to the examples. In the examples, comparative examples and manufacturing examples, the physical properties of the photosensitive resin composition are measured and evaluated according to the following methods.

[Measurement and evaluation methods] (1) Weight average molecular weight

The weight average molecular weight (Mw) of each resin was determined by gel permeation chromatography (converted to standard polystyrene). The column used for the determination was the "Shodex 805M/806M series" manufactured by Showa Denko (Co., Ltd.), the standard monodisperse polystyrene was the "Shodex STANDARD SM-105" manufactured by Showa Denko (Co., Ltd.), the developing solvent was N-methyl-2-pyrrolidone, and the detector was the "Shodex RI-930" manufactured by Showa Denko (Co., Ltd.).

(2) Determination of the imidization index of the hardened film

A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputter-coated with 200 nm thick Ti and 400 nm thick Cu in sequence using a sputtering device (model L-440S-FHL, manufactured by CANON ANELVA). Then, a photosensitive resin composition prepared by the following method was spin-coated on the wafer using a coating developer (model D-Spin60A, manufactured by SOKUDO), and dried by heating at 110°C on a heating plate for 3 minutes to form a photosensitive resin layer with a thickness of about 15 μm. Using a photomask with a test pattern, the photosensitive resin layer was irradiated with an energy of 200 mJ/ ^cm2 by a Prisma GHI (manufactured by Ultratech) equipped with an i-ray filter.

The wafer with the concave-convex pattern formed on Cu was heated at 350°C for 2 hours in a nitrogen atmosphere using a temperature-programmed thermal furnace (model VF-2000, manufactured by Koyo Lindberg), thereby obtaining a hardened concave-convex pattern composed of a resin with a thickness of about 10μm on Cu.

The hardened concavoconvex pattern was measured using an ATR-FTIR measuring device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) and a Si prism, and the measurement was performed 50 times in the measurement range of 4000-700 cm ^-1 . The peak height near 1380 cm ^-1 (1350-1450 cm ^-1 , when there are multiple peaks, the peak intensity is the largest) and the peak height near 1500 cm ^-1 (1460-1550 cm ^-1 , when there are multiple peaks, the peak intensity is the largest) of the cured film were calculated.

(3) Determination of the imidization rate of photosensitive resin compositions

A sputtering device (model L-440S-FHL, manufactured by CANON ANELVA) was used to sequentially sputter-coat 200nm thick Ti and 400nm thick Cu on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25μm). Then, a coating developer (model D-Spin60A, manufactured by SOKUDO) was used to spin-coat the photosensitive resin composition prepared by the following method on the wafer, and dried at 110°C on a heating plate for 3 minutes to form a photosensitive resin layer with a thickness of about 10μm.

The photosensitive resin layer was measured using an ATR-FTIR measuring device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) and a Si prism, and the measurement was performed 50 times in the measurement range of 4000 to 700 cm ^-1 . The value obtained by calculating the peak height of the cured film at around 1380 cm ^-1 (1350-1450 cm ^-1 , the peak intensity is the largest when multiple peaks exist) and dividing it by the peak height at around 1500 cm ^-1 (1460-1550 cm ^-1 , the peak intensity is the largest when multiple peaks exist) is taken as the imidization index of the photosensitive resin layer. The value obtained by dividing the imidization index of the photosensitive resin layer of the resin composition of each Example and Comparative Example by the imidization index of the cured film formed by curing the resin composition at 350° C. is taken as the imidization rate.

(4) Resolution of hardened concave-convex pattern on Cu

A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputter-coated with 200 nm thick Ti and 400 nm thick Cu in sequence using a sputtering device (model L-440S-FHL, manufactured by CANON ANELVA). Then, a photosensitive resin composition prepared by the following method was spin-coated on the wafer using a coating developer (model D-Spin60A, manufactured by SOKUDO), and dried by heating at 110°C on a heating plate for 3 minutes to form a photosensitive resin layer with a thickness of about 25 μm. Using a photomask with a test pattern, the photosensitive resin layer was irradiated with an energy of 200 mJ/ ^cm2 by a Prisma GHI (manufactured by Ultratech) equipped with an i-ray filter. Then, the photosensitive resin layer was spray developed using cyclopentanone as a developer and a coating developer (model D-Spin60A, manufactured by SOKUDO) and rinsed with propylene glycol methyl ether acetate to obtain a concave-convex pattern on Cu.

The wafer with the concave-convex pattern formed on Cu was heated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-programmed thermal furnace (model VF-2000, manufactured by Koyo Lindberg), thereby obtaining a hardened concave-convex pattern composed of a resin with a thickness of about 20μm on Cu.

The produced concave-convex pattern is observed under an optical microscope to find the size of the smallest opening pattern. At this time, if the area of the opening of the obtained pattern is more than 1/2 of the opening area of the corresponding pattern mask, it is considered to be resolved. Based on the length of the mask opening side corresponding to the opening with the smallest area among the resolved openings (the size of the opening pattern), the resolution is measured according to the following evaluation criteria.

(Evaluation criteria)

"Excellent": The minimum opening pattern size is less than 25μm

"Good": The minimum opening pattern size is greater than 25μm and less than 30μm

"Qualified": The minimum opening pattern size is greater than 30μm and less than 35μm

"Unqualified": The minimum opening pattern size is greater than 35μm.

(5) Determination of relative dielectric constant (Dk) and dielectric loss tangent (Df)

A sputtering device (model L-440S-FHL, manufactured by CANON ANELVA) was used to sputter-coat 100nm thick aluminum (Al) on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25μm) to prepare a sputter-coated Al wafer substrate.

The negative photosensitive resin composition was spin-coated on the above-mentioned sputtered Al wafer substrate using a spin coater (model D-spin60A, manufactured by SOKUDO), and dried by heating at 110°C for 180 seconds to form a spin-coated film. Thereafter, the entire surface was exposed to ghi rays at an exposure amount of 600mJ/ ^cm2 using an aligner (PLA-501F, manufactured by Canon), and heat-cured at 230°C for 2 hours in a nitrogen atmosphere using a longitudinal thermal furnace (model VF-2000B manufactured by Koyo Lindberg) to form a cured film. The film thickness of the cured film was measured by the following method. The hardened film was cut into 80 mm long and 60 mm wide or 40 mm long and 30 mm wide using a wafer dicing machine (manufactured by DISCO, model name DAD-2H/6T), immersed in a 10% hydrochloric acid aqueous solution and peeled off from a silicon wafer to prepare a film sample.

For the film samples, the relative dielectric constant (Dk) and dielectric loss tangent (Df) at 10, 28, 40, and 60 GHz were measured using the resonance perturbation method. The details of the measurement method are as follows.

(Measurement method)

Perturbation method: split cylindrical resonator method

(Device structure)

Network analyzer: PNA Network analyzer E5224B

(Made by Agilent technologies)

Split cylindrical resonator: CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measured frequency: about 10GHz), CR-728 (manufactured by Kanto Electronics Application Development Co., Ltd., measured frequency: about 28GHz), CR-740 (manufactured by Kanto Electronics Application Development Co., Ltd., measured frequency: about 40GHz), CR-760 (manufactured by Kanto Electronics Application Development Co., Ltd., measured frequency: about 60GHz)

(6) Absorbance

A manual spin coater (ELS306MA, manufactured by SEBACS) was used to spin coat the negative photosensitive resin composition on quartz glass (50 mm long, 50 mm wide, 1 mm thick), and dried 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.

The obtained spin-coated film was measured using an ultraviolet visible (UV-VIS) spectrophotometer (UV-1800, manufactured by Shimadzu Corporation). The absorbance at 365nm was measured and converted to 1μm according to the Lambert-Beer law to obtain the absorbance.

[(A) Production of polyimide precursors] <Production Example 1> ((A) Synthesis of polyimide precursor (polymer A-1))

Place 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) in a 2-liter separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and add 79.1 g of pyridine while stirring at room temperature to obtain a reaction mixture. After the heat of the reaction ends, cool to room temperature and let stand for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then a suspension of 93.0 g of 4,4'-oxydiphenylamine (ODA) suspended in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst ^TM 15" manufactured by Organo Co., Ltd.) 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 filtered and vacuum dried to obtain a powdered polymer A-1.

The weight average molecular weight (Mw) of the polymer A-1 was measured to be 22,000. The imide group concentration of each repeating unit of the polyimide obtained from polymer A-1 was 27.4wt%.

<Production Example 2> (Synthesis of polyimide precursor (polymer A-2))

In the above-mentioned Preparation Example 1, 175.9 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (BAPP) was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as the method described in Preparation Example 1 to obtain polymer A-2.

The weight average molecular weight (Mw) of the polymer A-2 was measured to be 24,000. The imide group concentration of each repeating unit of the polyimide obtained from polymer A-2 was 19.4wt%.

<Production Example 3> (Synthesis of polyimide precursor (polymer A-3))

In the above-mentioned Preparation Example 1, 169.9 g of bis{4-(4-aminophenoxy)phenyl}ketone (BAPK) was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as the method described in Preparation Example 1 to obtain polymer A-3.

The weight average molecular weight (Mw) of the polymer A-3 was measured to be 21,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-3 was 21.5wt%.

<Production Example 4> (Synthesis of polyimide precursor (polymer A-4))

In the above-mentioned Preparation Example 1, 260.2 g of 4,4'-(4,4'-isopropyldiphenoxy) 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 reaction was carried out in the same manner as the method described in Preparation Example 1, thereby obtaining polymer A-4.

The weight average molecular weight (Mw) of the polymer A-4 was measured to be 29,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-4 was 15.0wt%.

<Production Example 5> (Synthesis of polyimide precursor (polymer A-5))

In the above-mentioned Preparation 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 reaction was carried out in the same manner as the method described in Preparation Example 1, thereby obtaining polymer A-5.

The weight average molecular weight (Mw) of the polymer A-5 was measured to be 28,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-5 was 16.3wt%.

<Production Example 6> (Synthesis of polyimide precursor (polymer A-6))

In the above-mentioned Preparation Example 1, 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 was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as the method described in Preparation Example 1, thereby obtaining polymer A-6.

The weight average molecular weight (Mw) of the polymer A-6 was measured to be 24,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-6 was 17.0wt%.

<Production Example 7> (Synthesis of polyimide precursor (polymer A-7))

In the above-mentioned Preparation 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 reaction was carried out in the same manner as the method described in Preparation Example 1, thereby obtaining polymer A-7.

The weight average molecular weight (Mw) of the polymer A-7 was measured to be 24,000. The imide group concentration of each repeating unit of the polyimide obtained from polymer A-7 was 17.1wt%.

<Production Example 8> (Synthesis of polyimide precursor (polymer A-8))

In the above-mentioned Preparation Example 1, 219.3 g of 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl}propane (MBAPP) was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as the method described in Preparation Example 1 to obtain polymer A-8.

The weight average molecular weight (Mw) of the polymer A-8 was measured to be 25,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-8 was 18.7 wt%.

<Production Example 9> (Synthesis of polyimide precursor (polymer A-9))

In the above-mentioned Preparation Example 1, 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of ODA. The reaction was carried out in the same manner as the method described in Preparation Example 1 to obtain polymer A-9.

The weight average molecular weight (Mw) of the polymer A-9 was measured to be 24,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-9 was 26.8wt%.

<Production Example 10> (Synthesis of polyimide precursor (polymer A-10))

In the above-mentioned Preparation Example 1, 260.2 g of 4,4'-(4,4'-isopropyldiphenoxy) 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 reaction was carried out in the same manner as the method described in Preparation Example 1, thereby obtaining polymer A-10.

The weight average molecular weight (Mw) of the polymer A-10 was measured to be 23,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-10 was 19.1wt%.

<Production Example 11> (Synthesis of polyimide precursor (polymer A-11))

Put 260.2g of BPADA into a 2-liter separable flask, add 400ml of γ-butyrolactone under a nitrogen atmosphere, and add m-TB while stirring at room temperature to obtain a polyamide solution.

Then, the mixture was stirred at 185°C for 4 hours until the theoretical amount of water was removed and then cooled to room temperature to obtain polymer A-11.

The weight average molecular weight (Mw) of the polymer A-11 was measured to be 22,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-11 was 19.1wt%.

<Production Example 12> (Synthesis of polyimide precursor (polymer A-12))

Place 155.1 g of ODPA in a 2-liter separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and add 79.1 g of pyridine while stirring at room temperature to obtain a reaction mixture.

Next, the reaction mixture was cooled to -10°C, and while the temperature was maintained at -10°C, 124.4 g of SOCl2 was added over 60 minutes. Then, while stirring, a suspension of 93.0 g of 4,4'-oxydiphenylamine (ODA) suspended in 350 ml of γ-butyrolactone was added over 60 minutes. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified by mixing an anion exchange resin ("Amberlyst ^TM 15" manufactured by Organo Co., Ltd.) and a cation exchange resin ("IRA96SB" manufactured by Organo Co., Ltd.) 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 filtered and vacuum dried to obtain a powdered polymer A-12.

The weight average molecular weight (Mw) of the polymer A-12 was measured to be 9,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-12 was 27.4wt%.

<Production Example 13> (Synthesis of polyimide precursor (polymer A-13))

In the above-mentioned Preparation Example 12, 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used as 93.0 g of ODA. The reaction was carried out in the same manner as the method described in Preparation Example 1, thereby obtaining polymer A-13.

The weight average molecular weight (Mw) of the polymer A-13 was measured to be 8,000. The imide group concentration of each repeating unit of the polyimide obtained from the polymer A-13 was 26.8wt%.

[Manufacturing of photosensitive resin composition]

The following compounds are used in the examples and comparative examples.

Photopolymerization initiator B-1: TR-PBG-304 (manufactured by Changzhou Qiangli Electronics Co., Ltd.)

Photopolymerization initiator B-2: TR-PBG-305 (manufactured by Changzhou Qiangli Electronics Co., Ltd.)

Photopolymerization initiator B-3: TR-PBG-3057 (manufactured by Changzhou Qiangli Electronics Co., Ltd.)

Organic compound C-1: (bis-2,4-pentanedioic acid) di-n-butanol titanium

Organic compound C-2: Titanium diisopropylate (ethyl acetate)

Solvent D-1: γ-butyrolactone (GBL)

Solvent D-2: dimethyl sulfoxide (DMSO)

<Implementation Example 1>

A negative photosensitive resin composition was prepared using the polyimide precursor A-2 in the following method, and the prepared composition was evaluated. Dissolved in (A) A-2 as a polyimide precursor: 100 g, (B) B-1 as a photopolymerization initiator: 5 g, and (D) GBL: 100 g. A small amount of GBL was then added to adjust the viscosity of the obtained solution to about 40 poise. The composition was then aged for 48 hours in an incubator IN601 (manufactured by Yamato Scientific Co., Ltd.) at 40°C to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in the following Table 1-1.

<Implementation Example 2>

A negative photosensitive resin composition identical to Example 1 was prepared except that the aging conditions were set to 40°C for 144 hours, and the same evaluation as Example 1 was performed. The results are shown in Table 1-1 below.

<Implementation Example 3>

A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 1 g of C-1 was added as the (C) organic compound and the aging conditions were set to 23°C for 48 hours, and the same evaluation as in Example 1 was performed. The results are shown in Table 1-1 below.

<Implementation Examples 4 to 21, Comparative Examples 1 to 12>

The negative photosensitive resin composition was prepared in the same manner as in Examples 1 to 3 except that the composition was prepared and aged according to the mixing ratios shown in Tables 1 and 2 below, and the same evaluation as in Example 1 was performed. In addition, in the table, the "-" for the aging temperature and aging time indicates that no aging was performed. The results are shown in Tables 1 and 2 below.

As shown in Tables 1 and 2, the imidization rate of the photosensitive resin composition of Examples 1 to 21 showed a higher value than that of the photosensitive resin composition of Comparative Examples 1 to 7, and 11 and 12. In Comparative Examples 8 and 9, the absorbance showed a higher value, and the resolution became "unqualified". In Comparative Example 8, the imidization rate was 52.6%, which was a value exceeding 50%. In Comparative Example 10, the resin composition gelled and could not be evaluated.

[Industrial availability]

By using the photosensitive resin composition of the present invention, a cured film having a high resolution of a thick film and exhibiting a low dielectric loss tangent can be obtained. Therefore, the photosensitive resin composition of the present invention can be well used in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multi-layer wiring substrates.

Claims (23)

A photosensitive resin composition comprising: (A) 100 parts by weight of a polyimide precursor represented by the following general formula (1);

{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 of 2 to 150, _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R1 and _R2 is a group represented by the following general formula (2):

(wherein, R ₃ , R ₄ and R ₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10)}(B) 0.5 to 10 parts by weight of a photosensitive agent; and (D) 100 to 300 parts by weight of a solvent; the peak intensity of the infrared absorption spectrum of the photosensitive resin layer before exposure obtained by ATR (Attenuated Total Reflection) method is divided by the peak intensity of 1380 cm ^-1 in the vicinity of 1500 cm The value obtained by dividing the imidization index of the photosensitive resin layer obtained by the peak intensity near ^-1 by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350°C, that is, the imidization rate b is 15%~50%, and in the polyimide of the cured film, the ratio of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic acid and diamine, that is, the imide group concentration a is 12wt%~30wt%. The photosensitive resin composition of claim 1, wherein the above-mentioned imide group concentration a and imidization rate b satisfy the following formula (1): 0.10≦a×(1-b)≦0.17 (1). The photosensitive resin composition of claim 1 or 2, wherein in the polyimide of the hardened film, the ratio of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic acid and diamine, i.e., the imide group concentration a, is 12wt%~24wt%. As in the photosensitive resin composition of claim 1 or 2, the imidization index of the polyimide cured film obtained by heating and curing at 350°C is 0.10~0.54. The photosensitive resin composition of claim 1 or 2, wherein the absorbance of the photosensitive resin layer obtained by coating the photosensitive resin composition on quartz glass and heating it at 110°C for 3 minutes is 0.02~0.09 per 1μm at 365nm. The photosensitive resin composition of claim 1 or 2, wherein _Y1 in the general formula (1) is represented by the following formula:

{wherein, 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 one of the following formulae:

}. The photosensitive resin composition of claim 6, wherein the _Y1 is represented by the following formula:

or

or

The photosensitive resin composition of claim 1 or 2, wherein _X1 in the above general formula (1) is represented by the following formula:

{wherein, 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 one of the following formulae:

}. The photosensitive resin composition of claim 8, wherein the _X1 is represented by the following formula:

or

The photosensitive resin composition of claim 1 or 2 further comprises (C) at least one organic compound selected from an organic titanium compound or an organic zirconium compound: 0.01 to 5 parts by weight. As in claim 10, the photosensitive resin composition, wherein the above-mentioned (C) organic compound is an organic titanium compound. The photosensitive resin composition of claim 10, wherein the organic titanium compound is at least one compound selected from the group consisting of tetraalkoxy titanium compounds, titanium chelate compounds, titanium acylate compounds, and titanocene compounds. As in claim 12, the photosensitive resin composition, wherein the organic titanium compound is a titanium chelate or a tetraalkoxy titanium having two or more alkoxy groups. A photosensitive resin composition as claimed in claim 1 or 2, which is used to form an interlayer insulating film for a redistribution layer. The photosensitive resin composition of claim 1 or 2 further comprises (E) monomer: 0.5-15 parts by weight. As in claim 15, the photosensitive resin composition, wherein the above-mentioned (E) monomer contains at least one group selected from the group consisting of hydroxyl groups and amino groups. A method for preparing a photosensitive resin composition as claimed in any one of claims 1 to 16, comprising the following steps: a step of mixing the above-mentioned (A) polyimide precursor, the above-mentioned (B) photosensitive agent, and the above-mentioned (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%. A method for producing a polyimide cured film comprises the following steps (1) to (5): (1) coating a photosensitive resin composition as described in any one of claims 1 to 15 on a substrate to form a photosensitive resin layer on the substrate; (2) heating and drying the obtained photosensitive resin layer; (3) exposing the heated and dried photosensitive resin layer; (4) developing the exposed photosensitive resin layer; and (5) heating the developed photosensitive resin layer to form a polyimide cured film. As in claim 18, the manufacturing method of polyimide cured film, wherein the dielectric loss tangent of the polyimide cured film is 0.0021~0.007 when measured at 10 GHz using a perturbation split cylindrical resonator method. A method for manufacturing a polyimide cured film as claimed in claim 18 or 19, wherein the dielectric loss tangent of the polyimide cured film is 0.0021 to 0.008 when measured at 28 GHz using a perturbation split cylindrical resonator method. A method for manufacturing a polyimide cured film as claimed in claim 18 or 19, wherein the dielectric loss tangent of the polyimide cured film measured at 40 GHz using a perturbation split cylindrical resonator method is 0.0021 to 0.008. A method for manufacturing a polyimide cured film as claimed in claim 18 or 19, wherein the dielectric loss tangent of the polyimide cured film is 0.0021 to 0.009 when measured at 60 GHz using a perturbation split cylindrical resonator method. A method for producing a polyimide cured film is a method for producing a polyimide cured film using the following photosensitive resin composition, wherein the photosensitive resin composition comprises: (A) 100 parts by weight of a polyimide precursor represented by the following general formula (1);

{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 of 2 to 150, _R1 and _R2 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R1 and _R2 is a group represented by the following general formula (2):

(wherein, R ₃ , R ₄ and R ₅ are 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)}(B) a photosensitive agent: 0.5 to 10 parts by weight; and (D) a solvent: 100 to 300 parts by weight. The above-mentioned manufacturing method comprises the following steps (1) to (5): (1) applying the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate; (2) heating, drying and desolventizing the obtained photosensitive resin layer; (3) exposing the desolventized photosensitive resin layer; (4) developing the exposed photosensitive resin layer; and (5) heating the developed photosensitive resin layer to form a polyimide cured film; the imidization rate of the photosensitive resin layer before exposure obtained by heating, drying and desolventizing in step (2) is 15-50%.