TWI881618B - Photosensitive resin composition, cured film using the same and method for producing the same, and semiconductor device - Google Patents

Abstract

The present invention provides a photosensitive resin composition capable of forming a cured film that can achieve low dielectric properties (low dielectric loss tangent and low dielectric constant), high residual film rate, and ensures specified copper adhesion and specified heat resistance. A photosensitive resin composition contains (A) at least one component selected from polyimide precursors and polyimide, (B) a photopolymerization initiator, (C) a solvent, and (D) an allyl group-containing compound represented by the following general formula (1): (In the formula, _n1 is 0 or 1. When _n1 is 0, _R1 is a hydrogen atom or a monovalent non-polymerizable organic group. When _n1 is 1, _R1 is a divalent organic group).

Description

Photosensitive resin composition, cured film using the same and method for producing the same, and semiconductor device

The present invention relates to a photosensitive resin composition, a hardened film using the same, a method for producing the same, and a semiconductor device.

In the past, polyimide resins, polybenzoxazole resins, and phenolic resins with excellent heat resistance, electrical properties, and mechanical properties have been used in insulating materials for electronic parts, passivation films for semiconductor devices, surface protection films, and interlayer insulating films. Among these resins, photosensitive resin compositions provide a method of easily forming a heat-resistant relief pattern film by coating, exposure, development, and curing of the composition through closed-loop treatment (imidization, benzoxazoleization) and thermal crosslinking. Compared with the previous non-photosensitive materials, this photosensitive resin composition can easily achieve a significant reduction in steps, and therefore can be preferably used in the manufacture of semiconductor devices.

Semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards in various ways depending on their purpose. Previously, components were usually made by wire bonding, which uses thin wires to connect the external terminals (pads) of the component to the lead frame. However, as components are becoming faster and faster, and the operating frequency has reached GHz, the difference in the wiring length of each terminal during installation will affect the operation of the component. Therefore, in the installation of components for high-end applications, the length of the mounting wiring must be accurately controlled, and it is difficult to meet this requirement in wire bonding.

Therefore, a flip chip mounting has been proposed, which is to form a redistribution layer on the surface of a semiconductor chip, form bumps (electrodes) thereon, and then flip the chip (flip-chip) and mount it directly on a printed circuit board. In this flip chip mounting, the wiring distance can be accurately controlled, so it is used in high-end components for processing high-speed signals, and because of its smaller mounting size, it is used in mobile phones, etc., and the demand is rapidly expanding. Recently, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed (for example, refer to patent document 1), which is to cut the wafer completed in the pre-step to produce a single chip, rearrange the single chip on a support and seal it with a mold resin, and form a redistribution layer after peeling off the support. In fan-out wafer-level packaging, the redistribution layer is formed with a thinner film thickness, so it has the following advantages: it is easy to reduce the height of the package, and it is easy to achieve high-speed transmission and low cost.

In recent years, with the significant increase in information communication volume, it is necessary to seek higher-speed communication than the previous level, and it is necessary to switch to the fifth-generation communication (5G) with a frequency of more than 3 GHz, or the communication in the ultra-high frequency band of near-millimeter band (20 GHz to 30 GHz) to millimeter band (30 GHz and above) which can easily ensure a wider bandwidth. Therefore, not only the printed circuit board, but also the semiconductor chip mounted on the substrate is required to cope with high frequency. Therefore, in order to reduce transmission loss, a front-end module (FEM) for transmitting and receiving radio waves and an antenna system package (AiP) that integrates the antenna has been developed (for example, refer to patent document 2). In AiP, the wiring length is shorter, so the transmission loss that increases in proportion to the wiring length can be suppressed. However, with the increase in communication bandwidth, the redistribution material is required to have low dielectric properties. In addition, in AiP, multiple layers of redistribution layers are required as in the previous FOWLP, so the redistribution layer is also required to be flat. In order to make the redistribution layer flat, it is expected that the redistribution material has low shrinkage during heat curing, that is, the residual film rate of the redistribution layer (the residual film rate after curing) is higher. Furthermore, from the perspective of the reliability of semiconductor devices, it is also required to suppress the delamination between the redistribution layer and the copper and copper alloy wiring. In order to prevent delamination, it is desirable to ensure the specified copper adhesion in the initial stage before the reliability test and after the reliability test. In addition, in order to suppress delamination caused by the high temperature during the reliability test, it is desirable to reduce the thermal expansion of the redistribution layer material, that is, it is desirable for the redistribution layer material to ensure the specified heat resistance.

In order to reduce the transmission loss in the high frequency band, two methods can be considered: a method of reducing dielectric loss and a method of reducing conductor loss. For example, as a method of reducing dielectric loss, a method of using polyimide having specific side chains is known (for example, refer to Patent Document 3). In addition, as a method of increasing the residual film rate of the redistribution layer, a method of adding a specific crosslinking agent (a crosslinking agent containing multifunctional (meth)acrylate) to the resin is known (for example, refer to Patent Document 4). Furthermore, as a method for ensuring the close contact between the redistribution layer and the wiring, a method of adding a specific photoacid generator to the resin is known (for example, refer to Patent Document 5). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2005-167191 [Patent Document 2] U.S. Patent Application Publication No. 2016/0104940 [Patent Document 3] International Publication No. 2019/044874 [Patent Document 4] Japanese Patent Publication No. 2021-152634 [Patent Document 5] Japanese Patent Publication No. 2005-336125

[The problem the invention is trying to solve]

Polyimide has excellent insulation and thermomechanical properties, so it tends to have higher material reliability. On the other hand, due to the polar functional groups derived from the imide group, the polar functional groups added to achieve photosensitization, and the influence of additives, it tends to have higher dielectric constants and dielectric loss tangents, which is considered a problem.

The photosensitive resin composition described in Patent Document 3 has the following problem: the measurement frequency is a relatively low 1 GHz, so the performance is insufficient when used as a redistribution layer of AiP for high-frequency purposes. In addition, the photosensitive resin composition described in Patent Document 4 has the following problem: due to the influence of a large amount of multifunctional (meth)acrylate added as a crosslinking agent, there is a concern about the deterioration of dielectric properties at high frequencies. Furthermore, the photosensitive resin composition described in Patent Document 5 has the following problem: the photoacid generator assumed in Patent Document 5 is highly polar, so there is a concern about the deterioration of dielectric properties at high frequencies.

The purpose of the present invention is to provide a photosensitive resin composition that can form a hardened relief pattern that can suppress transmission loss in a high-band device and improve reliability by achieving low dielectric properties, high residual film rate, and ensuring specified copper adhesion and specified heat resistance, a hardened film using the same, a method for manufacturing the same, and a semiconductor device. [Technical means for solving the problem]

One aspect of the present invention is as follows. [1] A photosensitive resin composition comprising (A) at least one component selected from a polyimide precursor and a polyimide, (B) a photopolymerization initiator, (C) a solvent, and (D) an allyl group-containing compound represented by the following general formula (1): (wherein _n1 is 0 or 1, when _n1 is 0, _R1 is a hydrogen atom or a monovalent non-polymerizable organic group, and when _n1 is 1, _R1 is a divalent organic group). [2] The photosensitive resin composition of item 1, wherein the component (D) is a compound wherein _n1 is 0 and _R1 is a monovalent non-polymerizable organic group having 3 or more carbon atoms in the general formula (1). [3] The photosensitive resin composition of item 1 or 2, wherein the component (A) comprises a compound selected from the following general formula (2): [Chemical 2] (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, _n2 is an integer of 2 to 100, and _R2 and _R3 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms) and the following general formula (3): [Chemical 3] (wherein _X2 is a tetravalent organic group having 6 to 40 carbon atoms, _Y2 is a divalent organic group having 6 to 40 carbon atoms, and _n3 is an integer of 2 to 100). [4] A photosensitive resin composition according to any one of items 1 to 3, wherein at least one of _R2 and _R3 in the general formula (2) contains a group represented by the following general formula (4): [Chemical 4] (wherein, _R4 , _R5 and _R6 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). [5] The photosensitive resin composition of any one of items 1 to 4, further comprising (E) an imidization accelerator. [6] The photosensitive resin composition of any one of items 1 to 5, further comprising (F) a chelating agent containing a transition metal of a Group 4 element. [7] The photosensitive resin composition of any one of items 1 to 6, wherein at least one of _X1 and _X2 is represented by the following general formula (7): [Chemical 5] (wherein, Z is independently a divalent group selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, _R8 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m3 is independently an integer of 1 to 3, and _m4 is independently an integer of 1 to 4) and/or at least one of _Y1 and _Y2 is represented by the following general formula (8): [Chemistry 6] (wherein, Z is independently a divalent group selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, _R8 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m3 is independently an integer of 1 to 3, and _m4 is independently an integer of 1 to 4). [8] The photosensitive resin composition of any one of items 1 to 7, wherein the content of the allyl group-containing compound (D) is 0.5 to 30 parts by weight relative to 100 parts by weight of the component (A). [9] A method for producing a hardened film, comprising the following steps: a step of applying a photosensitive resin composition as described in any one of items 1 to 8 onto a substrate to form a photosensitive resin layer on the substrate; a step of heating and drying the obtained photosensitive resin layer; a step of exposing the photosensitive resin layer after arbitrary heating and drying; a step of developing the exposed photosensitive resin layer; and a step of heating the developed photosensitive resin layer to form a hardened film. [10] A cured film, which is a cured film of a photosensitive resin composition as described in any one of items 1 to 8, wherein the dielectric loss tangent of the cured film measured at 10 GHz using a perturbation split cylinder resonator method is 0.015 or less. [11] A cured film, which is obtained by applying the photosensitive resin composition as described in any one of items 1 to 8 on a substrate, performing an exposure treatment, a development treatment, and then a heat treatment, wherein the film thickness of the cured film after the heat treatment is 20 μm or more, and the dielectric loss tangent of the cured film measured at 10 GHz using a perturbation split cylinder resonator method is 0.015 or less. [12] A method for producing a cured film, comprising applying a photosensitive resin composition as described in any one of items 1 to 8 onto a substrate, performing an exposure process, a development process, and then a heat treatment to obtain a cured film, wherein the dielectric loss tangent of the cured film measured at 10 GHz using a perturbation split cylinder resonator method is less than 0.015. [13] A semiconductor device comprising a cured film of the photosensitive resin composition as described in any one of items 1 to 8. [14] A photosensitive resin composition comprising at least one component selected from a polyimide precursor and a polyimide, wherein the glass transition temperature Tg, the peel strength P from copper after a reliability test, and the dielectric loss tangent _tanδ10 measured at 10 GHz using a perturbation split cylinder resonator method satisfy the following formula: 0.25≦(Tg×P× _tanδ10 )≦1.00. [15] A photosensitive resin composition comprising at least one component selected from a polyimide precursor and a polyimide, wherein the glass transition temperature Tg, the peel strength P from copper after a reliability test, the dielectric loss tangent tanδ ₁₀ measured at 10 GHz using a perturbation split cylinder resonator method, and the dielectric constant ε ₁₀ of a cured film of the photosensitive resin composition satisfy the following formula: 1.0≦(Tg×P×tanδ ₁₀ ×ε ₁₀ )≦3.0. [Effect of the Invention]

According to the present invention, a photosensitive resin composition can be provided that can form a cured film (in one embodiment, a cured relief pattern) that can achieve low dielectric properties (low dielectric loss tangent and low dielectric constant), high residual film rate, and can ensure specified copper adhesion and specified heat resistance. In addition, according to the present invention, a cured film using the photosensitive resin composition, a method for manufacturing the same, and a semiconductor device can be provided.

The following is a detailed description of the implementation method of the present invention (hereinafter, also referred to as the present implementation method). 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 selected independently and can be the same or different from each other. In this specification, in the numerical range recorded in stages, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of another numerical range recorded in stages. In addition, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiment. Furthermore, the term "step" not only includes independent steps, but also includes steps that can achieve the function of the step even if they cannot be clearly distinguished from other steps.

<Photosensitive resin composition> The photosensitive resin composition of the present embodiment contains (A) at least one component selected from polyimide precursors and polyimide, (B) a photopolymerization initiator, (C) a solvent, and (D) an allyl-containing compound. The photosensitive resin composition of the present invention may further contain (E) an imidization accelerator, (F) a chelating agent containing a transition metal of a Group 4 element, and other components in addition to the above components as required.

(A) Component (A) Component is at least one selected from a polyimide precursor and a polyimide. From the viewpoint of easily obtaining the effect of the present invention and easily realizing a cured film with various excellent properties, component (A) preferably contains a compound selected from the following general formula (2): [Chemical 7] (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, _n2 is an integer of 2 to 100, and _R2 and _R3 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms) and the following general formula (3): [Chemical 8] (wherein X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n ₃ is an integer of 2 to 100)

In formula (2), at least one of _R2 and _R3 is preferably a reactive substituent that reacts with heat or light, and in particular, from the viewpoint of easily obtaining the effects of the present invention and easily realizing a cured film having various excellent properties, a group represented by the following general formula (4) is more preferably included: [Chemical 9] (wherein, R ₄ , R ₅ and R ₆ 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).

In formula (4), examples of the monovalent organic group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and isopropyl, preferably methyl. _R4 is preferably a hydrogen atom and a methyl group, and _R5 and _R6 are preferably a hydrogen atom and a methyl group, more preferably a hydrogen atom. _m1 is preferably an integer of 2 to 5, more preferably an integer of 2 to 3.

In formulas (2) and (3), _n2 and _n3 are preferably integers of 1 to 100, and more preferably integers of 3 to 70, from the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition.

In formulae (2) and (3), the tetravalent organic group represented by _X1 and _X2 is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of both heat resistance and photosensitivity, and more preferably a group in which _-COOR2 and _-COOR3 are adjacent to -CONH- (especially an aromatic group or an alicyclic aliphatic group). Specific examples of the tetravalent organic group represented by _X1 and _X2 include 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 (5): [Chemical 10] (wherein, _R7 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a carbonyl group having 1 to 10 carbon atoms, and a fluorine-containing carbonyl group having 1 to 10 carbon atoms, _m2 is an integer of 1 or 2, _m3 is an integer of 1 to 3, and _m4 is an integer of 1 to 4). The tetravalent organic groups represented by _X1 and _X2 may be one type or a combination of two or more types. The _X1 and _X2 groups having the structure represented by the above formula (5) are particularly preferred from the viewpoint of taking both heat resistance and photosensitivity into consideration.

In the above formulae (2) and (3), the divalent organic groups represented by _Y1 and _Y2 are preferably aromatic groups having 6 to 40 carbon atoms, for example, groups having a structure represented by the following general formula (6): [Chemical 11] (wherein, _R7 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m3 is an integer of 1 to 3, and _m4 is an integer of 1 to 4.) The divalent organic groups represented by _Y1 and _Y2 may be one type or a combination of two or more types. The _Y1 and _Y2 groups having the structure represented by the above formula (6) are particularly preferred from the viewpoint of taking both heat resistance and photosensitivity into consideration.

In component (A), at least one of _X1 and _X2 as skeleton components derived from tetracarboxylic dianhydride and _Y1 and _Y2 as skeleton components derived from diamine compounds preferably has two or more benzene rings. The two or more benzene rings may be bonded to each other directly or via a divalent or higher organic group. The number of benzene rings may be three or more, four or more, six or less, five or less, or four or less, and more preferably four. By making component (A) have such a structure, it is easy to maintain the resolution of the photosensitive resin composition, and therefore, there is a tendency to easily achieve low dielectric properties in the obtained hardened relief pattern.

In particular, from the viewpoint of low dielectric properties, it is preferred that at least one of _X1 and _X2 is represented by the following general formula (7): (wherein, Z is independently a divalent group selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, _R8 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m3 is independently an integer of 1 to 3, and _m4 is independently an integer of 1 to 4) and/or at least one of _Y1 and _Y2 is represented by the following general formula (8): [Chemical 13] (wherein, Z is independently a divalent group selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, _R8 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m3 is independently an integer of 1 to 3, and _m4 is independently an integer of 1 to 4).

The component (A) may have other reactive unsaturated bonds polymerized by heat or light at the end of the main chain, which are different from the reactive unsaturated bond side chains contained in the repeating units. Reactive unsaturated bonds refer to, for example, bonds that can react by heat or light and crosslink with each other. The reactive substituent has such a reactive unsaturated bond. Specific examples of structures having a site that also reacts with a carboxyl group and having a reactive substituent, and structures of the main chain ends modified with a reactive substituent are shown below. [Chemistry 14]

(A) Preparation method of component [tetracarboxylic dianhydride] As tetracarboxylic dianhydrides having tetravalent organic groups _X1 and _X2 having 6 to 40 carbon atoms which can be preferably used for preparing polyimide precursors or polyimides, in addition to tetracarboxylic dianhydrides derived from the above-mentioned structures, for example, pyromellitic anhydride, 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) diphthalic anhydride, 4,4'-bis(3,4-dicarboxydiphenoxy) benzophenone dianhydride, etc. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[Diamine compound] As diamine compounds having divalent organic groups _Y1 and _Y2 having 6 to 40 carbon atoms which can be preferably used for preparing polyimide precursors or polyimides, in addition to diamines derived from the structures listed above, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diamino-2,2'-dimethylbiphenyl, 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 sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 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 sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl sulfide, , 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 ] sulfide, 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 sulfide, 9,9-bis(4-aminophenyl)fluorene, and bis{4-(4-aminophenoxy)phenyl}ketone, and those in which a portion of the hydrogen atoms on the benzene ring is substituted with an alkyl chain such as a methyl group or an ethyl group, such as 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamine compound is not limited to these. These diamine compounds may be used alone or in combination of two or more.

[Terminal reactive substituent-introducing compound] As a compound for introducing a reactive substituent into the terminal of the main chain of a polyimide precursor or polyimide (terminal reactive substituent-introducing compound), for example, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethoxy)ethyl isocyanate, 1,1-(diacryloyloxymethyl)ethyl isocyanate, allylamine, methacryloyl chloride, and mixtures thereof, etc. However, the terminal reactive substituent-introducing compound is not limited to them. The terminal reactive substituent-introducing compound may be used alone or in combination of two or more.

[Reaction solvent] As a reaction solvent for synthesizing a polyimide precursor or polyimide, it is preferred that the raw material tetracarboxylic dianhydride and the first substituent-introducing compound described below, as well as the acid/ester body as the product, are completely dissolved. More preferred is a solvent that can also completely dissolve the polyimide precursor as the amide condensation product of the acid/ester body and diamine. Examples include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. As for specific examples thereof, as ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. can be cited. As esters, for example, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, etc. can be cited. As lactones, for example, γ-butyrolactone, etc. can be cited. As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc. can be cited. As halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc. can be cited. As hydrocarbons, for example, hexane, heptane, benzene, toluene, xylene, etc. can be cited. They can be used alone or in combination of two or more as needed.

In order to improve the adhesion between the photosensitive resin layer formed on the substrate by coating the photosensitive resin composition 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 component (A).

[Synthesis of polyimide precursor] The polyimide precursor (polyamic acid ester) of the present invention is obtained, for example, by the following steps: (step i) reacting the above-mentioned tetracarboxylic dianhydride containing a tetravalent organic group _X1 with a photopolymerizable unsaturated dibond alcohol and any saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester body); and (step ii) subjecting the acid/ester body to an amide condensation reaction with the above-mentioned diamine containing a _divalent organic group Y1.

(Step i) Preparation of Acid/Ester Forms A tetracarboxylic dianhydride containing a tetravalent organic group _X1 having 6 to 40 carbon atoms is reacted with a compound having a reactive substituent that reacts with heat or light (also referred to as a "substituent-introducing compound" in the present invention) to obtain an esterified tetracarboxylic acid (acid/ester form).

As the substituent-introducing compound (also referred to as "first substituent-introducing compound" in the present invention) preferably used for the synthesis of tetracarboxylic acid for esterification, there can be mentioned alcohols having a reactive substituent that reacts by heat or light. As the alcohols having a reactive substituent that reacts by heat or light, there can be mentioned, for example, 2-hydroxyethyl methacrylate (HEMA), 2-acryloxyethanol, 1-acryloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butyl acrylate. methacrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

As the saturated aliphatic alcohols which can be used arbitrarily together with the alcohols having a reactive substituent that reacts with heat or light, preferably saturated aliphatic alcohols having 1 to 4 carbon atoms are used. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and the like.

The tetracarboxylic dianhydride and the first substituent are introduced into the compound, preferably in the presence of an alkaline catalyst such as pyridine, preferably in an appropriate reaction solvent, and stirred and mixed at a temperature of 20 to 50° C. for 4 to 10 hours, thereby performing an esterification reaction of the anhydride to obtain the desired acid/ester.

(Step ii): Acid/ester body and diamine amide polycondensation reaction The diamine and the acid/ester body prepared above are subjected to a condensation reaction, thereby synthesizing polyamic acid ester. The acid/ester body is typically in a solution state dissolved in a reaction solvent after the acid/ester body is prepared by the above method. Preferably, an appropriate dehydrating condensation agent is added and mixed under ice cooling to convert the acid/ester body into a polyanhydride. Subsequently, a solvent that dissolves or disperses the diamine is added dropwise thereto to cause the two to undergo amide polycondensation, thereby obtaining polyamic acid ester. Diaminosiloxanes can be used together with the above diamines having a divalent organic group _Y1 . Examples of the dehydration condensation agent include dicyclohexylcarbodiimide (DCC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. By the above method, a polyanhydride as an intermediate is obtained.

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

The weight average molecular weight of the polyimide precursor is preferably 3,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000, from the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment, when measured by gel permeation chromatography (GPC) in terms of polystyrene conversion weight average molecular weight. 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 relief pattern are good, so it is preferred. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to use the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[Synthesis of Polyimide] The polyimide of the present invention is obtained by subjecting the tetracarboxylic dianhydride or its acid/ester containing the tetravalent organic group _X2 to a condensation reaction with the diamine containing the divalent organic group _Y2 to imidization.

From the viewpoint of increasing the acylation rate of imide, the tetracarboxylic dianhydride used in the synthesis of polyimide is preferably in the form of acid dianhydride rather than acid/ester. For example, tetracarboxylic dianhydride containing a tetravalent organic group _X2 with a carbon number of 6 to 40 and an excess amount of a diamine compound containing a divalent organic group _Y2 with a carbon number of 6 to 40 can be subjected to a condensation reaction and heated for acylation. The conditions for imidization are not limited, and for example, heating at 160°C to 300°C for 1 to 10 hours is sufficient. The higher the acylation rate of imide, the better, and there is no limitation, for example, it is preferably 90% or more, 95% or more, and more preferably 99% or more or 100%.

After the imidization reaction is completed, the water-absorbing byproduct of the dehydration condensation agent coexisting in the reaction solution is filtered and separated as needed, and then a suitable poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, is added to the solution containing the polymer component to precipitate the polymer component, and then the re-dissolution and re-precipitation operations are repeated as needed. After the polymer is purified, it is vacuum dried to isolate the target polyimide. In order to improve the degree of purification, the polymer solution can be passed through a column filled with an anion and/or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

The weight average molecular weight of the polyimide is preferably 3,000 to 150,000, more preferably 4,000 to 50,000, and particularly preferably 5,000 to 40,000, from the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment, when measured by gel permeation chromatography (GPC) in terms of polystyrene conversion weight average molecular weight. If the weight average molecular weight is 3,000 or more, the mechanical properties are good, so it is preferred. On the other hand, if it is 150,000 or less, the solubility in the solvent, the dispersibility in the developer, and the resolution performance of the relief pattern are good, so it is preferred. The conditions for gel permeation chromatography are the same as those described above.

(B) Photopolymerization initiator (B) Photopolymerization initiator is a compound that can generate free radicals by active light, thereby polymerizing compounds containing ethylenically unsaturated groups. Examples of initiators that generate free radicals by active light include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide. Examples thereof include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michelle's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-thiophenylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-thiophenyl-propanone-1, and propylene benzophenone. , 4-benzoyl-4'-methyldiphenyl sulfide and other aromatic ketones; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ether compounds; benzoin, methyl benzoin, ethyl benzoin and other benzoin compounds; 1,2-octanedione, 1-[4-(phenylthio)-phenyl]-, 2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (BASF JAPAN (co., Ltd.), Irgacure Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (Changzhou Qiangli Electronic New Materials Co., Ltd., PBG305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetyl oxime) (Nikko Chemtech (stock company), TR-PBG-326) and other oxime ester compounds; benzyl dimethyl ketal and other benzyl derivatives; 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and other acridine derivatives; N-phenylglycine and other N-phenylglycine derivatives; coumarin compounds; oxazole compounds; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and other phosphine oxide compounds. The above-mentioned (B) photopolymerization initiator can be used alone or in combination of two or more.

In this embodiment, (B) the photopolymerization initiator is preferably an oxime ester compound, and more preferably a compound selected from the group consisting of the following general formula: [Chemical 15] (wherein, _R9 is an alkyl group having 1 to 12 carbon atoms, phenyl or tolyl, _R10 and _R11 are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, phenyl or tolyl, and _R12 is -H, -OH, -COOH, -O( _CH2 )OH, -O( _CH2 ) _2OH , -COO( _CH2 )OH or -COO( _CH2 ) _2OH ), [Chemical 16] (wherein, R ₁₃ is independently an alkyl group having 1 to 6 carbon atoms, R ₁₄ is NO ₂ or ArCO (Ar is an aryl group), R ₁₅ and R ₁₆ are independently an alkyl group having 1 to 12 carbon atoms, phenyl or tolyl), and [Chemical 17] (wherein, R ₁₇ is an alkyl group having 1 to 6 carbon atoms, R ₁₈ is an organic group having an acetal bond, and R ₁₉ and R ₂₀ are independently an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group).

The amount of the photopolymerization initiator (B) is preferably 0.5 to 30 parts by weight, more preferably 2 to 15 parts by weight, relative to 100 parts by weight of the component (A). The above amount is preferably 0.5 parts by weight or more from the viewpoint of sensitivity or patterning properties, and is preferably 30 parts by weight or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

(C) Solvent (C) Solvent is preferably a solvent that can evenly dissolve or suspend (A) component and (B) photopolymerization initiator. Examples of such solvents include: γ-butyrolactone, dimethyl sulfoxide, tetrahydrofuran methanol, ethyl acetylacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more.

The above solvent is used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of component (A), depending on the desired coating film thickness and viscosity of the photosensitive resin composition. When the solvent contains an alcohol without an olefinic double bond, the content of the alcohol without an olefinic double bond in the entire solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the alcohol without an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition tends to be good, and when it is 50% by mass or less, the solubility of component (A) tends to be good.

(D) Allyl-containing compound (D) The allyl-containing compound is represented by the following general formula (1): (In the formula, _n1 is 0 or 1. When _n1 is 0, _R1 is a hydrogen atom or a monovalent non-polymerizable organic group. When _n1 is 1, _R1 is a divalent organic group).

The mechanism by which low dielectric properties, high residual film rate, and specified copper adhesion and specified heat resistance can be achieved by making the photosensitive resin composition contain (A) to (C) components and (D) allyl-containing compounds is not certain, but the inventors speculate as follows. The (D) allyl-containing compound has an allyl group, so when the photosensitive resin composition is heated (for example, above 150°C), a thermal crosslinking reaction can be generated between the (A) component and the (D) allyl-containing compound; between the (D) allyl-containing compounds; and between the (D) allyl-containing compound and the following other components. Thus, the (D) allyl-containing compound will not completely volatilize in the heat curing step, but a certain amount will remain in the film after heat curing, which is believed to result in the effect of ensuring low dielectric properties, high residual film rate, and specified heat resistance. On the other hand, allyl groups have lower free radical reactivity than (meth)acrylic groups. Therefore, by allowing the above-mentioned allyl groups to exist, it is possible to prevent highly polar compounds such as the substituent-introducing compound of the (A) component from remaining excessively in the film in the exposure step or the heating step, which is believed to result in the effect of ensuring low dielectric properties and specified copper adhesion. Furthermore, unlike epoxy groups, allyl groups do not generate highly polar functional groups during crosslinking, so it is believed that low dielectric properties are easily exhibited.

In the present embodiment, when _n1 in the general formula (1) is 0, _R1 is a hydrogen atom or a monovalent non-polymerizable organic group. The above-mentioned non-polymerizable organic group may have 1 to 30 carbon atoms, and may be an alkyl group having 1 to 30 carbon atoms. From the viewpoint of low dielectric properties, _R1 is preferably a carbon number of 3 or more. From the viewpoint of ensuring both low dielectric properties and the specified heat resistance, it is preferably a monovalent non-polymerizable organic group having 3 to 30 carbon atoms, more preferably a carbon number of 7 to 15 carbon atoms, and preferably an alkyl group. In the case of a carbon number of 1 or more, the ratio of low polarity sites in the compound is high, so it is easy to express low dielectric properties. In the case of an alkyl group having less than 30 carbon atoms, the ratio of soft sites in the compound is low, so it is easy to maintain heat resistance. In the case where R ₁ is not a non-polymerizable organic group but a polymerizable organic group such as an allyl group, a (meth)acryl group or an epoxy group, the above-mentioned thermal crosslinking reaction proceeds excessively, and a highly polar compound such as a substituent-introducing compound of the (A) component remains excessively in the film, or a highly polar functional group is generated during crosslinking. It is believed that the result is that although a high residual film rate and high heat resistance are achieved, the dielectric properties are deteriorated. Furthermore, it is believed that due to the excessive presence of the residue in the film, the interaction between the polymer chain and copper is hindered, and the copper adhesion is reduced. However, according to the present embodiment in which n ₁ in the general formula (1) is 0 and R ₁ is a hydrogen atom or a non-polymerizable organic group, excessive thermal crosslinking reaction can be prevented, and therefore it is believed that low dielectric properties can be achieved. In addition, it is considered that the decrease in copper adhesion can be prevented, and the predetermined copper adhesion and the predetermined heat resistance can be ensured. Therefore, the allyl group-containing compound of the present embodiment preferably has two allyl groups when _n1 is 0.

In the present embodiment, when _n1 in the general formula (1) is 1, _R1 is a divalent organic group. The divalent organic group may be a group having 1 to 30 carbon atoms, or may be an alkyl group having 1 to 30 carbon atoms. According to the present embodiment in which two isocyanuric acid rings having an allyl group are linked by _R1 , crosslinking is performed at an appropriate density, and therefore it is considered that excessive thermal crosslinking reaction can be suppressed. As a result, it is considered that even if there are 4 allyl groups, low dielectric properties, high residual film rate, assurance of prescribed copper adhesion, and assurance of prescribed heat resistance can be taken into account.

As described above, as a feature of the present embodiment, it can be cited that by having a crosslinking group that is easier to show dielectric properties than a (meth)acryl group or an epoxy group and a non-polymerizable organic group in one molecule, the crosslinking reaction proceeds at an appropriate density, and low dielectric properties and the assurance of specified heat resistance can be taken into account. In this effect, the crosslinking group is not limited to an allyl group, and even if it is a diene group, a styryl group, an ethynyl group, or other thermal crosslinking groups, low dielectric properties and the assurance of specified heat resistance can be taken into account.

(D) The allyl group-containing compound has an isocyanuric acid ring and thus has a stable structure. This stable structure is considered to be one of the main reasons for obtaining the effects of the present embodiment described above. Furthermore, due to this stable structure, the heat resistance of the photosensitive resin composition is easily improved and it is easy to show high solubility in the solvent used in the present invention.

As an example of the (D) allyl group-containing compound, the following structure can be cited: [Chemical 19] (In the formula, R is a hydrogen atom or a monovalent non-polymerizable organic group; when R is an alkyl group, the compound (D) is sometimes referred to as diallylalkyl isocyanurate, and when R is a methyl group, the compound (D) is sometimes referred to as diallylmethyl isocyanurate) [Chemistry 20] (wherein R is a divalent organic group).

Examples of commercially available products of such (D) allyl group-containing compounds include L-DAIC ( _n1 is 0, _R1 is an alkyl group having 3 or more carbon atoms), Me-DAIC ( _n1 is 0, _R1 is a hydrogen atom), DD-1 ( _n1 is 1, _R1 is a divalent non-polymerizable organic group) (all manufactured by Shikoku Chemical Industries, Ltd.), and diallylpropyl isocyanurate ( _n1 is 0, _R1 is an alkyl group having 2 carbon atoms) (manufactured by Tokyo Chemical Industry Co., Ltd.).

From the viewpoint of low dielectric properties, _n1 in the general formula (1) is more preferably 0. When _n1 in the general formula (1) is 0, the ratio of the highly polar site in the allyl group-containing compound (D) is small, so the effect on low dielectric properties becomes greater.

The content of the allyl group-containing compound (D) is preferably 0.5 to 30 parts by mass, more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the component (A). The above-mentioned amount is preferably 2 parts by mass or more from the viewpoint of more effectively achieving low dielectric properties and high residual film rate, and is preferably 20 parts by mass or less from the viewpoint of compatibility with the solvent and the component (A).

(E) Imidization accelerator (E) Imidization accelerator can be added arbitrarily to achieve better low dielectric properties. The so-called imidization accelerator refers to a compound that promotes imidization during the heat curing process of the photosensitive resin composition of the present invention. By using it, the substituent-introduced compound of the (A) component is easily separated at an early stage and is easily volatilized before the crosslinking is excessively carried out.

As (E) imidization accelerator, there are the following forms: a form in which the mobility of the polymer chain during heat curing of the photosensitive resin composition is increased by addition, thereby promoting imidization; and a form in which the imidization is promoted by being an alkaline compound. As the former, in order to increase the mobility of the polymer chain during heat curing, a compound that melts in the heat curing temperature range and does not volatilize is preferred. For example, SR-3000 and PX-200 (both manufactured by Daihachi Chemical Industry Co., Ltd.) can be cited. As the latter, an alkaline compound is preferred, and from the viewpoint of preventing deterioration during storage, for example, diethanolaniline can be cited.

When the imidization accelerator (E) is added, the content thereof is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, relative to the component (A). When the content is within the above range, the above-mentioned effect obtained by adding the imidization accelerator (E) can be easily obtained.

(F) Chelating agent containing transition metal of Group 4 element (F) Chelating agent containing transition metal of Group 4 element can be added arbitrarily for the purpose of low dielectric properties and high heat resistance. By containing the above-mentioned chelating agent, there is no theoretical constraint, but the metal element contained in the organic compound containing the metal element coordinates with the carbonyl group derived from the ester group and/or carboxyl group of the polyimide precursor, thereby suppressing the molecular movement of the polymer chain, and it is believed that the result is that low dielectric properties can be achieved.

(F) The chelating agent of transition metal containing Group 4 element preferably contains at least one metal element selected from the group consisting of titanium and zirconium and an organic group in one molecule. As the organic group, a alkyl group or a alkyl group containing an impurity atom is preferred. By containing an organic group, the imidization rate of the polyimide precursor contained in the photosensitive resin composition is increased, and the dielectric properties of the cured film are easily reduced. As the chelating agent of transition metal containing Group 4 element that can be used, for example, an organic group is bonded to a titanium atom or a zirconium atom via a covalent bond or an ionic bond, that is, an organic titanium compound or a zirconium compound.

Specific examples of organic titanium compounds or zirconium compounds are shown in the following I) to VII): I) As chelate compounds having two or more alkoxy groups as organic groups, there can be cited: titanium bis(acetylacetone)diisopropoxide, titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-pentanedioate)di(n-butyl alcohol), titanium bis(2,4-pentanedioate)diisopropoxide, titanium bis(tetramethylpimelate)diisopropoxide, titanium bis(ethyl acetylacetate)diisopropoxide, and compounds in which the titanium atoms of these compounds are replaced with zirconium atoms.

II) Examples of the tetraalkoxy compound include titanium tetra(n-butanol), titanium tetraethanol, titanium tetra(2-ethylhexanol), titanium tetraisobutanol, titanium tetraisopropanol, titanium tetramethylol, titanium tetramethoxypropanol, titanium tetramethylphenol, titanium tetra(n-nonanol), titanium tetra(n-propanol), titanium tetrastearyl alcohol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], and compounds wherein the titanium atom of these compounds is substituted with a zirconium atom.

III) Titanium cyclopentadienyl or zirconium cyclopentadienyl compounds include, for example, titanium pentamethylcyclopentadienyltrimethoxide, titanium bis(η ⁵ -2,4-dicyclopentadien-1-yl)bis(2,6-difluorophenyl)bis(η ⁵ -2,4-dicyclopentadien-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.

IV) Examples of the monoalkoxy compound include titanium tri(dioctylphosphate) isopropoxide, titanium tri(dodecylbenzenesulfonate) isopropoxide, and compounds wherein the titanium atom of these compounds is substituted with a zirconium atom.

V) Examples of the titanium oxide or zirconium oxide compound include bis(glutaric acid)titanium oxide, bis(tetramethylpimelic acid)titanium oxide, phthalocyanine oxidetitanium oxide, and compounds in which the titanium atom of these compounds is substituted with a zirconium atom.

VI) Examples of the titanium tetraacetylpyruvate or zirconium tetraacetylpyruvate compound include titanium tetraacetylpyruvate and compounds in which the titanium atom of these compounds is substituted with a zirconium atom.

VII) As the titanium ester coupling agent, for example, tri(dodecylbenzenesulfonyl)titanium isopropyl ester and the like can be cited.

In the above I) to VII), the case where the organic titanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds is preferred from the viewpoint of obtaining better dielectric properties. Particularly preferred are titanium bis(acetylacetonato)diisopropoxide, titanium tetraacetylacetonate, titanium bis(ethylacetylacetonate)diisopropoxide, titanium tetra(n-butoxide), and titanium bis(η ⁵ -2,4-dicyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl). From the viewpoint of compatibility with the solvent used in the present invention, titanium bis(acetylacetonate)diisopropoxide and titanium tetraacetylacetonate are more preferred.

When an organic titanium compound or zirconium compound is added, the content thereof is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to component (A). If the content is 0.01 parts by weight or more, the imidization rate of the resin composition and the dielectric properties of the cured film are likely to be good, while if the content is 5 parts by weight or less, the storage stability is likely to be excellent, which is preferred.

(G) Other components The photosensitive resin composition may further contain components (other components) other than the above-mentioned components (A) to (F). Examples of other components include: resin components other than component (A), organic compounds containing metal elements other than transition metals of Group 4 elements, silane coupling agents, free radical polymerizable compounds other than the above-mentioned (D) allyl-containing compounds, thermal crosslinking agents other than the above-mentioned (D) allyl-containing compounds, fillers, sensitizers, thermal polymerization inhibitors, azole compounds, and hindered phenol compounds.

Examples of the resin component include polyamide, polyazole, polyazole precursor, phenol resin, polyamide, epoxy resin, silicone resin, acrylic resin, etc. The amount of the resin component is preferably in the range of 0.01 to 20 parts by weight relative to 100 parts by weight of component (A).

As a photosensitive resin composition, in order to improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain a silane coupling agent. Examples of such compounds include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-isocyanatopropyltriethoxysilane and the like. Such silane coupling agents may be used alone or as a mixture of two or more.

The content of the silane coupling agent in the resin composition is preferably 0.2 mass % to 10 mass % relative to 100 mass parts of the component (A). From the viewpoint of copper adhesion, it is more preferably 1 mass % to 8 mass %, and further preferably 2 mass % to 6 mass %.

As a photosensitive resin composition, in order to improve the resolution of the relief pattern and the residual film rate after curing during thermal curing, the photosensitive resin composition may arbitrarily contain (D) a free radical polymerizable compound other than an allyl group-containing compound. As such a compound, 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, but examples thereof include: di(meth)acrylates of ethylene glycol or polyethylene glycol headed by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, di(meth)acrylates of propylene glycol or polypropylene glycol, di(meth)acrylates or tri(meth)acrylates of glycerol, cyclohexane di(meth)acrylate, di(meth)acrylate of 1,4-butanediol, and di(meth)acrylates of 1,4-butanediol. Compounds such as (meth)acrylate, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of neopentyl glycol, di(meth)acrylate of bisphenol A, (meth)acrylamide, derivatives thereof, trihydroxymethylpropane tri(meth)acrylate, di(meth)acrylate or tri(meth)acrylate of glycerol, di(meth)acrylate, tri(meth)acrylate or tetra(meth)acrylate of pentaerythritol, ethylene oxide or propylene oxide adducts of these compounds. Among these free radical polymerizable compounds, it is preferred to have three or more free radical polymerizable groups from the viewpoint of increasing the residual film rate after curing. These free radical polymerizable compounds may be used alone or as a mixture of two or more.

The content of the free radical polymerizable compound in the resin composition is preferably 0.5 to 50% by mass relative to 100 parts by mass of component (A). From the viewpoint of improving resolution and residual film rate after curing, it is more preferably 5 to 40% by mass, and further preferably 10% to 30% by mass.

In order to improve the residual film rate after curing, the photosensitive resin composition may optionally contain a thermal crosslinking agent other than the above-mentioned (D) allyl group-containing compound.

The so-called thermal crosslinking agent refers to a compound that undergoes addition reaction or polycondensation reaction by heat. These reactions are produced by the combination of component (A) and the thermal crosslinking agent, the thermal crosslinking agents with each other, and the thermal crosslinking agent and the following other components. The reaction temperature is preferably above 150°C.

Examples of the thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, cyclohexane compounds, dibutylene imide compounds, allyl compounds other than the allyl group-containing compounds (D) above, and blocked isocyanate compounds. From the viewpoint of improving the residual film rate after curing, the thermal crosslinking agent (F) preferably contains nitrogen atoms.

As examples of alkoxymethyl compounds, the following compounds can be cited. [Chemistry 22]

Examples of epoxy compounds include epoxy compounds containing a bisphenol A type group or hydrogenated bisphenol A diglycidyl ether (e.g., Epolight 4000 manufactured by Kyoei Chemical Co., Ltd.). Examples of the cyclohexane compound include 1,4-bis{[(3-ethyl-3-cyclohexanebutyl)methoxy]methyl}benzene, bis[1-ethyl(3-cyclohexanebutyl)methyl ether, 4,4'-bis[(3-ethyl-3-cyclohexanebutyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-cyclohexanebutylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-cyclohexanebutylmethyl)ether, diethylene glycol bis(3-ethyl-3-cyclohexanebutylmethyl)ether, bis(3-ethyl-3-cyclohexanebutylmethyl)ether, 1,3-bis[(3-ethyloxycyclobutane-3-yl)methoxy]benzene, OXT121 (trade name manufactured by Toagosei Co., Ltd.), OXT221 (trade name manufactured by Toagosei Co., Ltd.), etc. Examples of the bis(cis-butenediamide) compounds include 1,2-bis(cis-butenediamide)ethane, 1,3-bis(cis-butenediamide)propane, 1,4-bis(cis-butenediamide)butane, 1,5-bis(cis-butenediamide)pentane, 1,6-bis(cis-butenediamide)hexane, 2,2,4-trimethyl-1,6-bis(cis-butenediamide)hexane, N,N'-1,3-phenylenebis(cis-butenediamide), 4-methyl-N, N'-1,3-phenylenebis(cis-butenediamide), N,N'-1,4-phenylenebis(cis-butenediamide), 3-methyl-N,N'-1,4-phenylenebis(cis-butenediamide), 4,4'-bis(cis-butenediamide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(cis-butenediamide)diphenylmethane or 2,2-bis[4-(4-cis-butenediamidephenoxy)phenyl]propane. Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenylsulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, triallyl citrate, and the like. Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Co., Ltd., Takenate B-882N manufactured by Mitsui Chemicals Co., Ltd., 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden Co., Ltd.), toluene diisocyanate-based blocked isocyanates (e.g., Takenate B-830, etc.), 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Blonate PMD-OA01 and PMD-MA01 manufactured by Taiyoung Industries, etc.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Coronate BI-301, 2507 and 2554 manufactured by Tosoh, etc.), isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951 and 7990 manufactured by Baxenden, etc.). Among them, blocked isocyanate or dibutylene diimide compounds are preferred from the viewpoint of storage stability. The thermal crosslinking agent may be used alone or in combination of two or more.

The content of the thermal crosslinking agent in the resin composition is preferably 0.2 to 40 parts by mass relative to 100 parts by mass of component (A). From the viewpoint of improving low dielectric properties and residual film rate after curing, it is more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass.

In order to increase the residual film rate after curing, the photosensitive resin composition may optionally contain fillers. The so-called fillers are not limited as long as they are inert substances added to improve strength or various properties.

From the viewpoint of suppressing the increase in viscosity when forming a resin composition, the filler is preferably in a particle shape. Examples of the particle shape include needle-shaped, plate-shaped, spherical, etc., but from the viewpoint of suppressing the increase in viscosity when forming a resin composition, the filler is preferably in a spherical shape.

Examples of needle-shaped fillers include wollastonite, potassium titanate, chrysocolla, aluminum borate, and needle-shaped calcium carbonate. Examples of plate-shaped fillers include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-shaped calcium carbonate. Examples of spherical fillers include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, and barium titanate. Among them, silica, alumina, titanium oxide, and barium titanate are preferred from the viewpoint of electrical properties or storage stability when formed into a resin composition, and silica and alumina are more preferred. These fillers may be used alone or in combination of two or more.

The size of the filler is preferably 5 to 1000 nm, more preferably 10 to 1000 nm, when the filler is spherical, the primary particle size is defined as the size, and when the filler is plate-shaped or needle-shaped, the length of the long side is defined as the size. If it is 10 nm or more, there is a tendency to become sufficiently uniform when formed into a resin composition, and if it is 1000 nm or less, photosensitivity can be imparted. From the perspective of imparting photosensitivity, it is preferably 800 nm or less, more preferably 600 nm or less, and particularly preferably 300 nm or less. From the perspective of adhesion or uniformity of the resin composition, it is preferably 15 nm or more, more preferably 30 nm or more, and particularly preferably 50 nm or more.

The content of the filler in the resin composition is preferably 1 to 20 vol% relative to the total volume of the resin composition. From the perspective of dielectric properties, it is preferably 5 to 20 vol%. From the perspective of resolution, it is further preferably 5 to 10 vol%.

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-dimethyl Aminocinnamylene dihydroindanone, p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene)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-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4 -Phenylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazol, 2-benzylthiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used alone or in combination of plural kinds (e.g., 2 to 5 kinds). The amount of the sensitizer to be formulated is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of the component (A) having a polyamic acid ester structure or a polyimide structure.

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-catechol, phenothiocyanate, 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. These thermal polymerization inhibitors may be used alone or as a mixture of two or more.

The amount of the thermal polymerization inhibitor to be added is preferably in the range of 0.005 to 12 parts by weight based on 100 parts by weight of the component (A) in terms of sensitivity characteristics or patterning properties.

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, and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used alone or in combination 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 component (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 component (A), discoloration of the surface of copper or copper alloy is suppressed when the photosensitive resin composition is formed on copper or copper alloy, while if it is 20 parts by mass or less, the sensitivity is excellent, which is preferred.

When a substrate containing copper or a copper alloy is used, the photosensitive resin composition may contain a hindered phenol compound in order to suppress discoloration of the substrate. 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'-methylene-bis( 4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], isocyanuric acid tris(3,5-di-tert-butyl-4-hydroxybenzyl)ester, 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[4-(1-ethyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1-butyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1-ethyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1-butyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1-ethyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1-butyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1-ethyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris[4-(1- 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris[2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris[2,4,6-(1H,3H,5H)-trione 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5 -trioxan-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-trioxan-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-trioxan-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-trioxan-2,4,6-(1H,3H,5H)-trione, trione, 1,3,5-tri(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri(4-tert-butyl-5-ethyl ... Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trioxathia-2,4,6-(1H,3H,5H)-trione is particularly preferred.

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 component (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of sensitivity characteristics. 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 component (A), for example, 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 the amount is 20 parts by mass or less, the sensitivity is excellent, so it is preferred.

<Curing film and its manufacturing method> The present invention also provides a method for manufacturing a curing film, which includes the step of converting a photosensitive resin composition into polyimide. The method for manufacturing a curing film of the present invention includes, for example, the following steps: The step of applying the photosensitive resin composition of the present invention on a substrate to form a photosensitive resin layer on the substrate; The step of heating and drying the obtained photosensitive resin layer; The step of exposing the photosensitive resin layer after arbitrary heating and drying; The step of developing the exposed photosensitive resin layer; and The step of heating the developed photosensitive resin layer to form a curing film.

The photosensitive resin composition used in the method for producing the cured film preferably contains 100 parts by weight of component (A), 0.5 to 30 parts by weight of a photosensitizer, and 100 to 1000 parts by weight of a solvent. It is more preferred that the photosensitive resin composition contains a photo-radical polymerization initiator as the photosensitizer, and it is further preferred that the photosensitive resin composition is a negative type.

The specific steps of the method for producing a cured film can be carried out according to the steps (1) to (5) of the method for producing a cured film described above. The typical aspects of each step are described below.

(1) Photosensitive resin layer formation step In this step, the photosensitive resin composition of the present invention is applied to a substrate and then dried as needed to form a photosensitive resin layer. As a coating method, a method previously used in coating a 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 spray coating method using a spray coater, etc.

(2) Heating and drying steps If necessary, the photosensitive resin composition film can be heated and dried. As drying methods, air drying, heating drying by an oven or a heating plate, vacuum drying, etc. can be used. In addition, the drying of the coating is preferably carried out under conditions where the polyimide precursor part (polyamide ester) of the (A) component in the photosensitive resin composition does not undergo imidization. Specifically, when air drying or heating drying is performed, drying can be carried out at 20°C to 140°C for 1 minute to 1 hour. In the above manner, a photosensitive resin layer can be formed on the substrate.

(3) Exposure step In this step, the photosensitive resin layer formed above is exposed. As an exposure device, for example, a contact aligner, a mirror projection exposure machine, a stepper, etc. are used. Exposure can be performed through a photomask or a reticle with a pattern or directly. The light used in the exposure is, for example, an ultraviolet light source.

After exposure, a post-exposure bake (PEB) and/or a pre-development bake at any combination of temperature and time may be performed as needed for the purpose of improving the sensitivity. The baking conditions are preferably in the range of 40 to 120°C and 10 to 240 seconds, but are not limited to this range as long as the properties of the negative photosensitive resin composition of this embodiment are not impaired.

(4) Development step In this step, the exposed photosensitive resin layer is developed to form a relief pattern. When the photosensitive resin composition is negative, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from previously known photoresist developing methods, such as a rotary spray method, an immersion method, and an immersion method accompanied by ultrasonic treatment. In addition, after development, for the purpose of preparing the shape of the relief pattern, post-development baking can be performed as needed by any combination of temperature and time. As the developer used in the development, for example, a good solvent for the negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are mixed, 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 may be used, for example, a combination of several solvents. It is preferred to perform the above-mentioned coating-developing steps in such a way that a photosensitive resin layer with a film thickness of 5 to 40 μm is obtained in the step of developing the exposed photosensitive resin layer.

(5) Cured film formation step In this step, the relief pattern obtained by the above-mentioned development is heated to disperse the photosensitive component and imidize the (A) component, thereby converting it into a hardened relief pattern containing polyimide. As a method of heat curing treatment, 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 control program. Heating can be performed at 160°C to 400°C for 30 minutes to 5 hours. As an ambient gas during heat curing, air can be used, and an inert gas such as nitrogen and argon can also be used. In the above manner, a hardened relief pattern (polyimide hardened film) can be produced.

The present invention also provides a cured film obtained from the photosensitive resin composition described above. From the viewpoint of suppressing transmission loss originating from the dielectric, the dielectric loss tangent of the cured film at a frequency of 10 GHz measured by a perturbation split cylinder resonator method is preferably 0.015 or less, and the lower the better.

In the present invention, from the viewpoint of suppressing transmission loss of devices used in high-speed communications, the cured film obtained from the photosensitive resin composition described above preferably has a film thickness of 20 μm or more. The film thickness of the cured film may be 100 μm or less.

The method for producing a cured film of the present invention, for example, comprises applying the photosensitive resin composition of the present invention on a substrate, performing an exposure process, a developing process, and then performing a heat treatment, and the dielectric loss tangent of the cured film when measured at 10 GHz by a perturbation split cylinder resonator method is preferably 0.015 or less, and the lower the better. The dielectric loss tangent may exceed 0. In addition, the dielectric constant of the cured film when measured at 10 GHz by a perturbation split cylinder resonator method is preferably 1.5 to 3.5. Furthermore, the dielectric constant and the dielectric loss tangent can be measured by the perturbation split cylinder resonator method shown in the following embodiment.

<Semiconductor device> The present invention also provides a semiconductor device having a hardened relief pattern obtained by using the photosensitive resin composition of the present invention by the above-mentioned method for manufacturing a hardened relief pattern (hardened film). That is, the semiconductor device includes a hardened film of the above-mentioned photosensitive resin composition. Therefore, in one aspect of the present embodiment, a semiconductor device is provided, which has a substrate as a semiconductor element and a hardened relief pattern of polyimide formed on the substrate by the above-mentioned method for manufacturing a hardened relief pattern. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-mentioned method for manufacturing a hardened relief pattern as part of the steps. The semiconductor device can be manufactured by the following method: the hardened embossed pattern formed by the above-mentioned hardened embossed pattern manufacturing method is used 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 having a bump structure, and is combined with a known semiconductor device manufacturing method.

The polyimide contained in the hardened relief pattern (hardened film) formed from the photosensitive resin composition preferably has the following general formula (9): [Chemical 23] (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 _n2 is an integer of 2 to 100) and/or the following general formula (3): [Chemical 24] (wherein X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n ₃ is an integer of 2 to 100)

In addition to being used in the semiconductor devices mentioned above, the photosensitive resin composition of the present invention can also be used for interlayer insulation of multi-layer circuits, covering layers of flexible copper foils, solder resists, liquid crystal alignment films, and the like.

The present invention also provides a cured film obtained from the photosensitive resin composition described above. From the perspective of transmission loss originating from the dielectric, the dielectric loss tangent tanδ ₁₀ of the cured film at a frequency of 10 GHz measured by the perturbation split cylinder resonator method is preferably 0.015 or less, and the lower the better. Furthermore, from the perspective of the reliability of the redistribution layer, the glass transition temperature Tg of the cured film is preferably higher, preferably above 190°C. By setting it to above 190°C, delamination or cracks between the redistribution layer and the copper and copper alloy wiring when exposed to high temperatures during reliability testing can be suppressed. Furthermore, the ease of peeling between the wiring layer and the copper and copper alloy wiring can also be expressed by the peeling strength P from the copper after the reliability test. The peeling strength P of the hardened film is preferably higher, preferably above 0.20 N/mm.

As a rewiring material for copper wiring used in high-speed transmission, it is preferred that the product of the glass transition temperature (Tg), the peel strength (P) with copper after reliability testing, and the dielectric loss tangent (tanδ ₁₀ ) at a frequency of 10 GHz (Tg×P×tanδ ₁₀ ) be within a certain range, preferably satisfying the following formula: 0.25≦(Tg×P×tanδ ₁₀ )≦1.00. By making Tg×P×tanδ ₁₀ a value within the range of the above formula, a polyimide cured material that is preferably used as a rewiring material for copper wiring used in high-speed transmission can be obtained. Tg×P×tanδ ₁₀ is more preferably 0.30 or more and 0.90 or less. When Tg×P×tanδ ₁₀ is 0.25 or more, the reliability is high, so it is suitable as a redistribution material for copper wiring. When Tg×P×tanδ ₁₀ is 1.00 or less, the transmission loss from the dielectric is small, so it is suitable for devices used in high-speed transmission. By using Tg and P, whose higher values contribute to high reliability, and tanδ ₁₀ , whose lower value contributes to low transmission loss, and taking their product, the range of hardened films with high reliability and suitable for devices used in high-speed transmission is specified.

According to the embodiment of the present invention, a cured film satisfying the range of 0.25≦(Tg×P×tanδ ₁₀ )≦1.00 is obtained. By virtue of the characteristics of the embodiment, i.e., having a crosslinking group that is easier to exhibit dielectric properties than a (meth)acrylic group or an epoxy group, and a non-polymerizable organic group in one molecule, the crosslinking reaction proceeds at an appropriate density, and low dielectric properties, a specified heat resistance, and a specified peel strength from copper after a reliability test are obtained. In this effect, the crosslinking group is not limited to an allyl group, and may also be other thermal crosslinking groups such as a diene group, a styryl group, and an ethynyl group.

As for the polyimide cured material which is preferred as the redistribution material of the copper wiring used in high-speed transmission, the glass transition temperature (Tg) and the peel strength (P) from copper after the reliability test and the dielectric loss tangent (tanδ ₁₀ ) at a frequency of 10 GHz, and the product of the dielectric constant (ε ₁₀ ) (Tg×P×tanδ ₁₀ ×ε) are preferably within a certain range, preferably satisfying the following formula: 1.0≦(Tg×P×tanδ ₁₀ ×ε ₁₀ )≦3.0. ε ₁₀ is an indicator of the ease of dielectric polarization of the dielectric. When ε ₁₀ is smaller, it helps to suppress the transmission loss from the dielectric. By making Tg×P×tanδ ₁₀ ×ε ₁₀ within the above range, a polyimide cured product that is preferably used as a redistribution material for copper wiring used in high-speed transmission can be obtained.

<Method for producing photosensitive resin composition> The method for producing the photosensitive resin composition of the present invention comprises: The step of producing component (A) by the method of the present invention as described in the above "Method for producing component (A)"; and The step of obtaining the photosensitive resin composition by mixing component (A), (B) a photopolymerization initiator, (C) a solvent, and (D) a specific allyl-containing compound. The above-mentioned (E) imidization accelerator, (F) a chelating agent containing a transition metal of a Group 4 element, and (G) other components may be optionally mixed. [Example]

The physical properties of the photosensitive resin compositions in the Examples, Comparative Examples, and Preparation Examples of the present invention were measured and evaluated according to the following methods.

<Measurement and evaluation methods> (1) Weight average molecular weight The weight average molecular weight (Mw) of diamine oligomers and copolymers was measured by gel permeation chromatography (standard polystyrene conversion). The column used in the measurement was Shodex 805M/806M series manufactured by Showa Denko Co., Ltd., the standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd., the developing solvent was N-methyl-2-pyrrolidone, and the detector was Shodex RI-930 manufactured by Showa Denko Co., Ltd.

(2) Dielectric constant (ε ₁₀ ) and dielectric loss tangent (tan δ ₁₀ ) A 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) was sputter-coated with 100 nm thick aluminum (Al) using a sputter coating device (L-440S-FHL model, manufactured by CANON ANELVA). In this way, a sputter-coated Al wafer substrate was prepared. A photosensitive resin composition prepared by the following method was spin-coated on the above-mentioned sputter-coated Al wafer substrate using a spin coating device (D-spin60A model, manufactured by SOKUDO Corporation), and heated and dried at 110°C for 360 seconds to form a photosensitive resin layer of about 37 μm. After that, the whole surface was exposed to ghi line with an exposure amount of 600 mJ/ ^cm2 using an alignment exposure machine (PLA-501F, manufactured by Cannon), and heat-curing treatment was performed at 230°C for 2 hours in a nitrogen environment using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B). In this way, a hardened film was made on the Al wafer. The hardened film was cut into 80 mm in length and 62 mm in width (for 10 GHz measurement) using a dicing machine (manufactured by DISCO, model name DAD-2H/6T). In addition, it was immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer to make a film sample (hardened film sample). The dielectric constant (ε ₁₀ ) and dielectric loss tangent (tan δ ₁₀ ) of the sample were measured at 10 GHz by the resonator perturbation method. The details of the measurement method are as follows.

(Measurement method) Resonator perturbation method (perturbation split cylinder resonator method) (Measurement sample humidity control) 23℃/50%RH static for 24 hours (Measurement conditions) 23℃/50%RH (Device configuration) Network analyzer: PNA Network analyzer N5224B (manufactured by KEYSIGHT) Split cylinder resonator: CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: about 10 GHz)

(3) Residual film rate A 6-inch silicon wafer (manufactured by Fujimi Electronic Industry 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 (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 (D-Spin60A, manufactured by SOKUDO), and heat-dried on a heating plate at 110°C for 360 seconds to form a photosensitive resin layer of about 37 μm. Thereafter, the entire surface was exposed to ghi rays at an exposure dose of 800 mJ/ ^cm2 using an alignment exposure machine (PLA-501F, manufactured by Cannon). Thereafter, the coating formed on the wafer was spray developed using cyclopentanone using a developer (D-SPIN636, manufactured by Dainippon Screen Manufacturing Co., Ltd., Japan). Furthermore, after rinsing with propylene glycol methyl ether acetate, the coating was dried by rotary drying. The thickness of the film after development was measured as film thickness 1. Furthermore, a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to heat and harden the developed film at 230°C for 2 hours in a nitrogen environment. The thickness of the film after the heat treatment was measured as film thickness 2. Using these film thicknesses, the residual film rate was calculated using the following formula, and the evaluation was performed based on the following criteria. Residual film rate (%) = (film thickness 2/film thickness 1) × 100 (Evaluation criteria) A: The residual film rate after curing is 85 or more to 100 B: The residual film rate after curing is 80 or more to less than 85 C: The residual film rate after curing is less than 80 In the present invention, it is considered that the residual film rate is preferably the result of B or above.

(4) Evaluation of copper adhesion A 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) was sputter-plated with 200 nm thick Ti and 400 nm thick Cu in sequence using a sputtering device (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 (D-Spin60A, manufactured by SOKUDO), and heat-dried on a hot plate at 110°C for 360 seconds to form a photosensitive resin layer of about 37 μm thickness. After that, the whole surface was exposed to ghi line with an exposure dose of 800 mJ/ ^cm2 using an alignment exposure machine (PLA-501F, manufactured by Cannon), and a heat curing treatment was performed at 230°C for 2 hours in a nitrogen environment using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to form a cured film on the Cu wafer. The film after heat treatment was evaluated for the bonding properties between the copper substrate and the cured resin coating based on the following criteria according to the cross cut method of the JIS K 5600-5-6 standard. (Evaluation criteria) A: The number of grids of the hardened resin coating film that is in contact with the substrate is 80 or more to 100 B: The number of grids of the hardened resin coating film that is in contact with the substrate is 60 or more to less than 80 C: The number of grids of the hardened resin coating film that is in contact with the substrate is 40 or more to less than 60 D: The number of grids of the hardened resin coating film that is in contact with the substrate is less than 40

(5) Evaluation of copper adhesion after reliability test A hardened film was formed on a wafer sputter-plated with Ti and Cu in the same steps as the copper adhesion evaluation described above. The hardened film was subjected to a reliability test for 168 hours at a temperature of 130°C and a humidity of 85%RH using a PCT device (manufactured by Hirayama Seisakusho, model name PC-422R8D). Afterwards, a tape (Evercel tape manufactured by Sekisui Chemical Industry) was attached to the hardened film, and the measured portion was cut into 5 mm wide with a cutter. The film was stretched at a speed of 100 mm/min using a tensile tester (manufactured by A&D Co., Ltd.: RTG-1210) to measure the 180° peel strength.

(6) Evaluation of heat resistance A hardened film was prepared on an Al wafer in the same manner as the above-mentioned dielectric constant (ε ₁₀ ) and dielectric loss tangent (tanδ ₁₀ ). The hardened film was cut into short strips of 3 mm in width using a dicing machine (manufactured by DISCO, model name DAD-2H/6T). The film was then immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer to prepare a film sample (hardened film sample). The obtained sample was heated from room temperature to 300°C at a heating rate of 10°C/min in a nitrogen environment using a thermomechanical analyzer (TMA) (TMA-60, manufactured by Shimadzu Corporation, Japan), and the glass transition temperature was measured.

<Production of component (A)> Synthesis of polymer A1 (polyimide precursor (polyamic acid ester)): 62 g of 4,4'-oxydiphthalic anhydride (ODPA) as an acid component was placed in a 1-liter separable flask, and 54 g of 2-hydroxyethyl methacrylate (HEMA) and 190 g of GBL were added. 32 g of pyridine was added while stirring at room temperature, and the mixture was heated at 50°C for 4 hours. After the heat generated by the reaction was terminated, the mixture was cooled to room temperature. The mixture was then left to stand for 16 hours to obtain a reaction mixture.

Next, under ice-cooling, a solution of 81 g of dicyclohexylcarbodiimide (DCC) dissolved in 81 g of GBL was added to the reaction mixture for 30 minutes while stirring, and then 30 g of GBL was added. Subsequently, a solution of 33 g of 4,4'-diaminodiphenyl ether (DADPE) as a diamine component and 106 g of GBL was added while stirring for 30 minutes. After further stirring at room temperature for 4 hours, 18 g of ethanol and 140 g of GBL were added and stirred for 30 minutes. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 2250 g of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered and dissolved in 1000 g of GBL to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst ^TM 15JWET" manufactured by Organo (Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 9200 g of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdered polymer A1. The weight average molecular weight (Mw) of the polymer A1 is 20,000.

Synthesis of polymer A2 (polyimide precursor (polyamide)): In the above-mentioned synthesis method of polymer A1, except that 104 g of 4,4'-(4,4'-isopropyldiphenyloxy)diphthalic anhydride (BPADA) was used instead of 62 g of ODPA, and 35 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 33 g of DADPE, the same method as described in the synthesis method of polymer A1 was used to obtain a solution of polymer A2. The weight average molecular weight (Mw) of the polymer A2 was measured and the result was 18,000.

Synthesis of polymer A3 (polyimide precursor (polyamic acid ester)): In the above-mentioned synthesis method of polymer A1, except that 68 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 33 g of DADPE, the same method as the method described in the synthesis method of polymer A1 was used to obtain a solution of polymer A3. The weight average molecular weight (Mw) of the polymer A3 was measured and the result was 24,000.

Synthesis of polymer A4 (polyimide): In a 0.5-liter separable flask equipped with a Dean-Stark tube and a condenser, 104 g of BPADA as an acid component, 64 g of m-TB as a diamine component, and 670 g of NMP as a solvent were added and dissolved while stirring. Then, 42.3 g of toluene was added and stirred, and the temperature was raised to 185°C under a nitrogen flow. After stirring at 185°C for 2.5 hours, the toluene in the system and the water generated by imidization were removed over 1.5 hours. Then, the mixture was cooled to room temperature to obtain a polymer A4 solution. The weight average molecular weight (Mw) of the polymer A4 was measured and found to be 7,000. The polymer A4 was subjected to ¹ H-NMR measurement, and the peak derived from the amide bond was compared with the peak derived from the aromatic ring of the polyimide to confirm the imide ring closure rate. The imide ring closure rate was 99% or more.

＜(B)～(F) ingredients＞ Photopolymerization initiator B1: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyl oxime) (trade name: PBG-3057, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) Photopolymerization initiator B2: 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (trade name: Irgacure Oxe02, manufactured by BASF JAPAN) Photopolymerization initiator B3: 2-benzyl-2-dimethylamino-1-(4-oxo-1-phenyl)-butanone-1 (trade name: Omnirad369, manufactured by IGM RESINS)

Solvent C1: γ-butyrolactone (GBL) Solvent C2: dimethyl sulfoxide (DMSO)

Compound D1: L-DAIC (manufactured by Shikoku Chemical Industries, Ltd.) Compound D2: Me-DAIC (manufactured by Shikoku Chemical Industries, Ltd.) Compound D3: DD-1 (manufactured by Shikoku Chemical Industries, Ltd.) Compound D4: DA-MGIC (manufactured by Shikoku Chemical Industries, Ltd.) Compound D5: TAIC (manufactured by Mitsubishi Chemical Co., Ltd.) Compound D6: NK ESTER A-9300 (manufactured by Shin-Nakamura Chemical Industries, Ltd.) Compound D7: Diallylpropyl isocyanurate (manufactured by Tokyo Chemical Industries, Ltd.) Compound D8: 1,3,5-tributyl-1,3,5-triazacyclohexane-2,4,6-trione (manufactured by Sigma-Aldrich Co., Ltd.)

Imidization accelerator E1: SR-3000 (manufactured by Daihachi Chemical Industries, Ltd.) Imidization accelerator E2: PX-200 (manufactured by Daihachi Chemical Industries, Ltd.) Imidization accelerator E3: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Chelating agent F1: ORGATIX TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.) Chelating agent F2: ORGATIX TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

<Example 1> As shown in the table, 100 g of polymer A1 as component (A) and 3 g of photopolymerization initiator B1 as component (B) were dissolved in a mixed solvent (weight ratio C1:C2=127:23) containing GBL and DMSO as solvent (C) to prepare a photosensitive resin composition solution. The composition was evaluated by the above method.

<Examples 2 to 17, Comparative Examples 1 to 5> Except for changing the types and amounts of the components as shown in the table, the photosensitive resin composition solution was prepared in the same manner as in Example 1 and evaluated.

[Table 1] Table 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 (A) Polymer (g) A1 100 100 100 100 100 100 100 A2 100 70 A3 100 A4 100 30 (B) Photopolymerization initiator (g) B1 3 3 3 3 3 3 3 3 3 B2 3 B3 3 (C) Solvent (g) C1 127 127 127 127 127 127 127 127 127 127 127 C2 twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three (D) Allyl-containing compounds (g) D1 15 15 15 15 15 15 15 5 20 D2 15 D3 D4 D5 D6 D7 15 D8 (E) Imidization accelerator (g) E1 E2 E3 (F) Chelating agent (g) F1 F2 ε10(10 gHz) 3.1 3.0 3.1 3.1 3.1 3.1 3.1 3.1 3.0 3.0 3.0 tanδ10(10 gHz) 0.014 0.007 0.009 0.006 0.006 0.014 0.014 0.015 0.013 0.015 0.015 Residual film rate after hardening (%) A A A A A A A B A A A Copper adhesion A A A A A A A A B A A Peak strength after reliability test 0.3 0.3 0.3 0.3 0.3 0.28 0.28 0.32 0.28 0.3 0.3 Tg 200 190 190 190 190 200 200 202 195 205 205 Tg*P*tanδ10 0.84 0.40 0.52 0.34 0.34 0.78 0.78 0.97 0.71 0.92 0.92 Tg*P*tanδ10*ε10 2.6 1.2 1.6 1.1 1.1 2.4 2.4 3.0 2.1 2.8 2.8 [Table 2] Table 2 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 (A) Polymer (g) A1 100 100 100 100 100 100 100 100 100 100 100 A2 A3 A4 (B) Photopolymerization initiator (g) B1 3 3 3 3 3 3 3 3 3 3 3 B2 B3 (C) Solvent (g) C1 127 127 127 127 127 127 127 127 127 127 127 C2 twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three (D) Allyl-containing compounds (g) D1 15 15 15 15 15 D2 D3 15 D4 15 D5 15 D6 15 D7 D8 15 (E) Imidization accelerator (g) E1 4 E2 4 E3 4 (F) Chelating agent (g) F1 4 F2 4 ε10(10 gHz) 3.3 3.0 3.0 3.1 3.0 3.0 3.1 3.3 3.2 3.2 3.0 tanδ10(10 gHz) 0.015 0.013 0.013 0.013 0.012 0.012 0.016 0.030 0.021 0.022 0.012 Residual film rate after hardening (%) A A A A A A C A A A B Copper adhesion B C C A C C A B C D B Peak strength after reliability test 0.3 0.2 0.2 0.35 0.3 0.3 0.38 0.34 0.3 0.2 0.1 Tg 205 190 190 200 210 210 210 230 230 230 180 Tg*P*tanδ10 0.92 0.49 0.49 0.91 0.76 0.76 1.28 2.35 1.45 1.01 0.22 Tg*P*tanδ10*ε10 3.0 1.5 1.5 2.8 2.3 2.3 4.0 7.7 4.6 3.2 0.6

In the above table, "Tg*P*tanδ ₁₀ " represents the product of the glass transition temperature (Tg), the peeling strength from copper after the reliability test (P), and the dielectric loss tangent (tanδ ₁₀ ) at a frequency of 10 GHz, and "Tg*P*tanδ ₁₀ *ε ₁₀ " represents the product of the glass transition temperature (Tg), the peeling strength from copper after the reliability test (P), the dielectric loss tangent (tanδ ₁₀ ) at a frequency of 10 GHz, and the dielectric constant (ε ₁₀ ).

As is clear from the table, in an embodiment, a photosensitive resin composition capable of forming the following hardened relief pattern can be provided, the hardened relief pattern can achieve low dielectric properties and high residual film rate, and can also ensure the specified copper adhesion and heat resistance. Specifically, in an embodiment, a photosensitive resin composition capable of forming the following hardened relief pattern can be provided, the hardened relief pattern achieves all of the following: dielectric loss tangent is 0.015 or less, dielectric constant is 3.1 or less, residual film rate evaluation result is "B" or more, initial copper adhesion evaluation result before reliability test is "C" or more, copper peel strength evaluation result after reliability test is 0.2 or more, and heat resistance (Tg) is 190°C or more.

On the other hand, the comparison example 1 in which the component (D) is not added has the following results: compared with the example, the residual film rate is lower and the dielectric loss tangent is higher. Moreover, in the comparison examples 2, 3 and 4 in which _R1 in formula (1) is a polymerizable functional group, the following results are obtained: the residual film rate and the heat resistance (Tg) are higher, and on the other hand, the dielectric loss tangent is higher than the example, and the initial copper adhesion before the reliability test is lower. Furthermore, in the comparison example 5 in which there is no crosslinking group in the molecule, the following results are obtained: compared with the example, the dielectric loss tangent is lower, and on the other hand, the residual film rate after curing is lower, the copper adhesion is lower, and the heat resistance is lower. From the above results, it can be seen that no sufficient results were obtained in the comparison examples.

In the embodiment and comparative examples 1 to 4, Tg is above 190°C, so thermal expansion at high temperatures is suppressed, and the copper adhesion does not decrease after the reliability test. On the other hand, the Tg in comparative example 5 is lower, so the copper adhesion decreases significantly after the reliability test. In the embodiment, the value of Tg×P×tanδ ₁₀ is within the range of 0.25 to 1.00, while it is greater than 1.00 in comparative examples 1 to 4, and the reliability is higher, but it is not suitable for use in devices used in high-speed communications. Moreover, in comparative example 5, it does not reach 0.25, and transmission loss can be suppressed in devices used in high-speed communications, but the reliability is lower. The same result is obtained for the value of Tg×P×tanδ ₁₀ ×ε _10. [Industrial Applicability]

The photosensitive resin composition of the present invention can be preferably used in the field of photosensitive materials useful in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (15)

A photosensitive resin composition comprises: (A) at least one component selected from a polyimide precursor and a polyimide, (B) a photopolymerization initiator, (C) a solvent, and (D) an allyl group-containing compound represented by the following general formula (1):

(wherein, _n1 is 0 or 1, when _n1 is 0, _R1 is a hydrogen atom or a monovalent non-polymerizable organic group, and when _n1 is 1, _R1 is a divalent organic group), the content of the allyl group-containing compound (D) is 0.5-30 parts by weight relative to 100 parts by weight of the above-mentioned component (A). The photosensitive resin composition of claim 1, wherein the component (D) is a compound wherein _n1 in the general formula (1) is 0 and _R1 is a monovalent non-polymerizable organic group having 3 or more carbon atoms. The photosensitive resin composition of claim 1 or 2, wherein the component (A) comprises a compound selected from the following general formula (2):

(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, _n2 is an integer of 2 to 100, and _R2 and _R3 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms) and the following general formula (3):

(wherein X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n ₃ is an integer of 2 to 100) The photosensitive resin composition of claim 1 or 2, wherein at least one of R ₂ and R ₃ in the general formula (2) contains a group represented by the following general formula (4):

(wherein, R ₄ , R ₅ and R ₆ 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). The photosensitive resin composition of claim 1 or 2 further contains (E) an imidization accelerator. The photosensitive resin composition of claim 1 or 2 further contains (F) a chelating agent containing a transition metal of a Group 4 element. The photosensitive resin composition of claim 1 or 2, wherein at least one of _X1 and _X2 is represented by the following general formula (7):

(wherein, Z is independently a divalent group selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, _R is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m is independently an integer of 1 to 3, and _m is independently an integer of 1 to 4) and/or at least one of _Y and _Y is represented by the following general formula (8):

(wherein, Z is independently a divalent group selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, _R8 is independently a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a alkyl group having 1 to 10 carbon atoms, and a fluorine-containing alkyl group having 1 to 10 carbon atoms, _m3 is independently an integer of 1 to 3, and _m4 is independently an integer of 1 to 4). A method for manufacturing a cured film, comprising the following steps: applying the photosensitive resin composition as claimed in claim 1 or 2 on a substrate to form a photosensitive resin layer on the substrate; exposing the obtained photosensitive resin layer; developing the exposed photosensitive resin layer; and heating the developed photosensitive resin layer to form a cured film. The method for manufacturing a cured film as claimed in claim 8 further includes the step of heating and drying the obtained photosensitive resin layer between the step of forming a photosensitive resin layer on the substrate and the step of exposing the photosensitive resin layer. A cured film, which is a cured film of a photosensitive resin composition as claimed in claim 1 or 2, and the dielectric loss tangent of the cured film measured at 10 GHz using a perturbation split cylinder resonator method is less than 0.015. A cured film obtained by applying the photosensitive resin composition of claim 1 or 2 on a substrate, performing exposure treatment, developing treatment, and then heating treatment, wherein the film thickness of the cured film after the heat treatment is greater than 20 μm, and the dielectric loss tangent measured at 10 GHz using a perturbation split cylinder resonator method is less than 0.015. A method for producing a cured film, wherein the photosensitive resin composition as claimed in claim 1 or 2 is applied to a substrate, subjected to exposure treatment, development treatment, and then heat treatment to obtain a cured film, and the dielectric loss tangent of the cured film measured at 10 GHz using a perturbation split cylinder resonator method is less than 0.015. A semiconductor device comprising a hardened film of the photosensitive resin composition of claim 1 or 2. The photosensitive resin composition of claim 1 contains at least one component selected from a polyimide precursor and a polyimide, and the cured film of the photosensitive resin composition has a glass transition temperature Tg, a peel strength P from copper after a reliability test, and a dielectric loss tangent _tanδ10 measured at 10 GHz using a perturbation split cylinder resonator method that satisfies the following formula: 0.25≦(Tg×P× _tanδ10 )≦1.00. The photosensitive resin composition of claim 1 contains at least one component selected from a polyimide precursor and a polyimide, and the glass transition temperature Tg, the peeling strength P from copper after a reliability test, the dielectric loss tangent tanδ ₁₀ measured at 10 GHz using a perturbation split cylinder resonator method, and the dielectric constant ε ₁₀ of a cured film of the photosensitive resin composition satisfy the following formula: 1.0≦(Tg×P×tanδ ₁₀ ×ε ₁₀ )≦3.0.