TWI857269B - Photosensitive resin composition, method for producing polyimide cured film using the same, and polyimide cured film - Google Patents

Abstract

The present invention provides a photosensitive resin composition having low dielectric properties and low moisture permeability and capable of forming a hardened relief pattern with high resolution. The photosensitive resin composition of the present invention comprises 100 parts by weight of at least one resin selected from polyimide and polyimide precursor, 0.5 to 10 parts by weight of a photosensitive agent, and 100 to 300 parts by weight of a solvent. The polyimide cured film obtained by heating and hardening the photosensitive resin composition at 350°C has an imide group concentration of 12 wt% to 26 wt%. The resin comprises a structure represented by the following general formula (14).

Description

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

The present invention relates to a photosensitive resin composition, a method for manufacturing a polyimide cured film using the same, and the polyimide cured film.

唑樹脂、酚樹脂等。該等樹脂之中，以感光性樹脂組合物之形態提供者可藉由該組合物之塗佈、曝光、顯影、及基於固化之閉環處理(醯亞胺化、苯并

唑化)或熱交聯容易地形成耐熱性之凸紋圖案皮膜。此種感光性樹脂組合物具有與先前之非感光型材料相比能夠大幅減少步驟之特徵，被用於製作半導體裝置。 Previously, the insulating materials of electronic parts, passivation films, surface protection films, and interlayer insulating films of semiconductor devices have used polyimide resins and polyphenylene sulfide resins with excellent heat resistance, electrical properties, and mechanical properties.

Among these resins, the photosensitive resin composition provides a photosensitive resin composition that can be coated, exposed, developed, and cured by ring-closing treatment (imidization, benzophenone

The photosensitive resin composition can be easily formed into a heat-resistant relief pattern film by azole treatment or thermal crosslinking. This photosensitive resin composition has the characteristic of greatly reducing the number of steps compared to previous non-photosensitive materials and is used in the manufacture of semiconductor devices.

Semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards in various ways according to their purpose. Previously, components were usually made by wire bonding, that is, thin metal wires were used to connect the external terminals (pads) of the components to the lead frame. However, as components are becoming 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 wire bonding is difficult to meet its requirements.

Therefore, flip chip mounting has been proposed, that is, a redistribution layer is formed on the surface of a semiconductor chip, and bumps (electrodes) are formed thereon, and then the chip is turned over (flip-chip) and mounted directly on a printed circuit board. Since the flip chip mounting can accurately control the wiring distance, it is used for high-end components that process high-speed signals or for mobile phones, etc. depending on the size of the mounting size, and the demand is rapidly expanding. Furthermore, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has recently been proposed (e.g., patent document 1), which is to cut the wafer that has completed the previous steps to produce a single chip, reconstruct the single chip on a support body, seal it with a mold resin, and peel off the support body to form a redistribution layer. In fan-out wafer-level packaging, since the redistribution layer is formed with a thinner film thickness, it has the advantages of being able to reduce the height of the package, and enabling high-speed transmission and low cost.

In recent years, with the significant increase in information communication volume, it is necessary to achieve higher-speed communication than the previous level, and it is necessary to shift to the fifth generation communication (5G) using frequencies above 3GHz or ultra-high frequency bands of near millimeter wave bands (20GHz~30GHz)~millimeter wave bands (above 30GHz) that can easily ensure wider bandwidths. Not only printed circuit boards, but also semiconductor chips mounted on the substrates need to correspond to high frequencies. Therefore, in order to reduce transmission losses, an antenna in package (AiP) has been developed that integrates a front-end module (FEM) for radio wave transmission and reception and an antenna (for example, refer to the following patent document 2). In AiP, since the wiring length is shorter, the transmission loss that increases in proportion to the wiring length can be suppressed.

Generally speaking, as the frequency of electrical signals increases, transmission loss increases. In order to reduce transmission loss in high frequency bands, there are two methods: reducing dielectric loss and reducing conductor loss. For the former, the photosensitive resin composition is required to have low dielectric properties (low dielectric loss tangent, low dielectric constant) (e.g., Patent Document 3). For the latter, the roughness of the metal redistribution layer must be reduced.

As an interlayer material for protecting the redistribution layer, the metal layer and the resin layer through the redistribution are required to have a high degree of adhesion from the perspective of not only low dielectric properties but also reliability. In particular, in recent years, the temperature for heat curing the redistribution layer is required to be relatively low. As such a photosensitive resin composition, for example, Patent Document 4 can be cited.

[Prior Art Literature] [Patent Literature]

[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. 2018-200470

In recent years, the types of supports have diversified due to the diversification of packaging and mounting technologies. In addition, the wiring layers have become multi-layered, so the dielectric constant and dielectric loss tangent (tanδ) of the insulating material used to form the wiring have become more affected. When the dielectric constant or dielectric loss tangent is high, the dielectric loss increases, so the transmission loss increases. Polyimide resin has high material reliability due to its excellent insulation performance and thermomechanical properties, but on the other hand, the situation where the dielectric constant or dielectric loss tangent is high due to the polar functional groups derived from the imide group, the addition of polar functional groups used for photosensitization, and the influence of additives is considered a problem. In addition, there are cases where the frequency dependence of the dielectric loss tangent becomes a problem, and it is considered that the lower the moisture permeability of the insulating layer, the better.

The purpose of the present invention is to provide a photosensitive resin composition having low dielectric properties and low moisture permeability and capable of forming a hardened relief pattern with high resolution, as well as a method for manufacturing a polyimide hardened film using the same and a polyimide hardened film.

Examples of implementation methods of the present invention are listed in the following items [1] to [19].

[1]

A photosensitive resin composition comprises: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5-10 parts by weight of a photosensitive agent; and (C) 100-300 parts by weight of a solvent. In the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350° C., the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit comprising a structure derived from tetracarboxylic dianhydride and diamine, i.e., the imide group concentration U, is 12 wt %-26 wt %. The resin comprises a structure represented by the following general formula (14):

{wherein, R ₁₅ is an organic group having 1 to 5 carbon atoms, R ₁₆ , R ₁₇ and R ₁₈ are each independently a single bond that can form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group having 6 to 10 carbon atoms and containing an aromatic ring, m ₉ is an integer selected from 1 to 4, m ₁₀ , m ₁₁ and m ₁₂ are each independently an integer selected from 0 to 4, Z ₂ is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the above-mentioned resin}.

[2]

For example, in the photosensitive resin composition of item 1, in the polyimide of the polyimide cured film obtained by heating and curing the above-mentioned photosensitive resin composition at 350°C, the total ratio of the molecular weight of aliphatic hydrocarbons to the molecular weight of the repeating units containing the structure derived from tetracarboxylic dianhydride and diamine compound, i.e., the aliphatic hydrocarbon concentration T is 4wt%~35wt%.

[3]

A photosensitive resin composition as in item 1 or 2, wherein the structure represented by general formula (14) is derived from a diamine.

[4]

A photosensitive resin composition as described in any one of items 1 to 3, wherein the resin is a polyimide precursor.

[5]

The photosensitive resin composition of item 4, wherein the polyimide precursor comprises a structure represented by the following general formula (4):

{wherein, _X1 is a tetravalent organic group having 6 to 40 carbon atoms, _Y1 is a divalent organic group having 6 to 40 carbon atoms, _n1 is an integer of 2 to 150, _R4 and _R5 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R4 and _R5 is a group represented by the following general formula (5)}

{wherein, R ₆ , R ₇ and R ₈ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10}.

[6]

A photosensitive resin composition comprises: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5-10 parts by weight of a photosensitizer; and (C) 100-300 parts by weight of a solvent. When the resin comprises a polyimide precursor, the polyimide precursor is represented by the following general formula (4):

{wherein, _X1 is a tetravalent organic group having 6 to 40 carbon atoms, _Y1 is a divalent organic group having 6 to 40 carbon atoms, _n1 is an integer of 2 to 150, _R4 and _R5 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R4 and _R5 is a group represented by the following general formula (5)}

{wherein, R ₆ , R ₇ and R ₈ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10}

The above resin comprises a structure represented by the following general formula (15):

{wherein, Rz each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and may form a ring structure, a represents an integer of 0 to 4, A each independently represents an oxygen atom or a sulfur atom, and B is one of the following formulae:

The above resin comprises a structure represented by the following general formula (14):

{wherein, R ₁₅ is an organic group having 1 to 5 carbon atoms, R ₁₆ , R ₁₇ and R ₁₈ are each independently a single bond that can form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group having 6 to 10 carbon atoms and containing an aromatic ring, m ₉ is an integer selected from 1 to 4, m ₁₀ , m ₁₁ and m ₁₂ are each independently an integer selected from 0 to 4, Z ₂ is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a linking portion to the main chain of the above-mentioned resin}.

[7]

A photosensitive resin composition comprising: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5 to 10 parts by weight of a photosensitive agent; and (C) 100 to 300 parts by weight of a solvent; the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C is In the amine, when the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic dianhydride and diamine is set as the imide group concentration U, and the ratio of the total molecular weight of the aliphatic hydrocarbon group is set as the aliphatic hydrocarbon group concentration T, U is 12wt%~26wt%, and satisfies the following formula (1): -12.6<U-T<16.0 (1).

[8]

A photosensitive resin composition comprises: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5-10 parts by weight of a photosensitive agent; and (C) 100-300 parts by weight of a solvent; in the IR (Infrared Radiation) spectrum of the polyimide obtained by heating and curing the polyimide precursor (A) at 230° C., the maximum peak intensity of the absorption peak in the range of 1450 cm ^-1 to 1550 cm ^-1 is defined as Ph ₁ , the peak intensity of the second intensity is defined as Ph ₂ , the peak intensity near 1380 cm ^-1 is defined as Im ₁ , and the peak intensity near 1550 cm -1 is defined as Ph 2 . When ₁ is normalized to 1, the following formula (2) is satisfied: 0.34≦Ph ₂ ×Im ₁ ≦1.2 (2).

[9]

A photosensitive resin composition as described in any one of items 1 to 8, wherein the resin is a reaction product of tetracarboxylic dianhydride and diamine.

[10]

A photosensitive resin composition as in item 9, wherein at least one of the tetracarboxylic dianhydrides and at least one of the diamines constituting the resin have an aliphatic hydrocarbon group.

[11]

A photosensitive resin composition as described in any one of items 1 to 10, further comprising (D) a silane coupling agent.

[12]

A photosensitive resin composition as described in any one of items 1 to 11, further comprising (E) a free radical polymerizable compound.

[13]

The photosensitive resin composition of item 12 is characterized in that: (E) the free radical polymerizable compound has an alkyl group.

[14]

The photosensitive resin composition of any one of items 1 to 13 further comprises (F) a thermal crosslinking agent.

[15]

A photosensitive resin composition as described in any one of items 1 to 14, further comprising (G) a filler.

[16]

A method for producing a polyimide cured film, comprising the following steps: applying a photosensitive resin composition as described in any one of items 1 to 15 on a substrate to form a photosensitive resin layer on the substrate; heating and drying the obtained photosensitive resin layer; exposing the heated and dried photosensitive resin layer; developing the exposed photosensitive resin layer; and heating the developed photosensitive resin layer to form a polyimide cured film.

[17]

As in the method for manufacturing a polyimide cured film of item 16, the coating and developing steps are performed in such a way that a photosensitive resin layer with a film thickness of 10 μm to 15 μm is obtained in the developing step, and the developing time during the developing is less than 30 seconds.

[18]

A polyimide cured film having a dielectric loss tangent of 0.003-0.014 at a frequency of 40 GHz obtained by a perturbation split cylindrical resonator method and satisfying the following formula (3): 3<tanδ ₄₀ ×WVTR<10 (3)

{wherein, tanδ ₄₀ represents the dielectric loss tangent at a frequency of 40 GHz obtained by the perturbation split cylindrical resonator method, and WVTR represents the moisture permeability of the polyimide cured film converted to a film thickness of 10 μm}.

[19]

A photosensitive resin composition as described in any one of items 1 to 15, wherein the photosensitive resin composition is used for redistribution layer purposes.

By using the photosensitive resin composition of the present invention, a cured resin film having excellent resolution of relief patterns and low dielectric properties, low moisture permeability, and good chemical resistance can be produced. By using a polyimide precursor having a specific terminal crosslinking group and aliphatic hydrocarbon group, the solubility of the pre-baked film in the developer is improved, thereby improving the resolution of the relief pattern. In addition, the hydrophobicity and crosslinking density in the cured film are improved, thereby reducing the moisture permeability and improving the chemical resistance. In addition, the exclusion volume is increased, thereby reducing the dielectric loss tangent.

Figure 1 is an example of the IR spectrum of polyimide obtained by curing the polyimide precursor at 230°C.

The following is a detailed description of the implementation of the present invention. In this specification, when there are multiple structures represented by the same symbol in the general formula in a molecule, unless otherwise specified, they are independently selected and may be the same or different. In addition, structures represented by the same symbol in different general formulas are also independently selected and may be the same or different unless otherwise specified.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention contains (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursors having a specific structure, (B) 0.5 to 10 parts by weight of a photopolymerization initiator, and (C) 50 to 500 parts by weight of a solvent. In addition, the photosensitive resin composition of the present invention may further contain (D) a silane coupling agent, (E) a compound containing an ethylenically unsaturated group, (F) a thermal crosslinking agent, (G) a filler, and other components as needed in addition to the above components.

[(A) Polyimide and polyimide precursor]

From the viewpoint of resolution, moisture permeability and low dielectric loss tangent, (A) at least one resin selected from polyimide and polyimide precursor preferably comprises a structure represented by the following general formula (14).

{wherein, R ₁₅ is an organic group having 1 to 5 carbon atoms, R ₁₆ , R ₁₇ and R ₁₈ are each independently a single bond that can form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group having 6 to 10 carbon atoms and containing an aromatic ring, m ₉ is an integer selected from 1 to 4, m ₁₀ , m ₁₁ and m ₁₂ are each independently an integer selected from 0 to 4, Z ₂ is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the above-mentioned resin}.

In the above general formula (14), _Z2 is preferably a structure selected from a single bond or an organic group having a heteroatom or an organic group having 1 to 13 carbon atoms, and the organic group having a heteroatom is preferably a structure selected from the following formula. The organic group having a heteroatom is an organic group having at least one heteroatom selected from N, O, P, S, Cl, I, and Br. Examples of the organic group include unsaturated hydrocarbons and saturated hydrocarbons, and more preferably saturated hydrocarbons. The organic group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.

By including the structure of the above general formula (14), a cured film with better resolution of relief patterns and lower moisture permeability can be obtained. Although theoretically not constrained, it is believed that by introducing an organic group into the aromatic ring, the solubility of the polyimide precursor in the developer is improved, and it is easy to ensure the contrast with the exposed part, and the resolution of the relief pattern is improved. In addition, although theoretically not constrained, it is believed that by introducing an organic group into the aromatic ring, the hydrophobicity of the film is improved, and it is not easy for moisture to pass through.

As an example of the structure of the above general formula (14), at least one structure selected from the group consisting of the following general formula (9) can be cited.

When the structure of the above formula (14) is derived from tetracarboxylic dianhydride when preparing polyimide and polyimide precursor, it is preferably composed of at least one structure selected from the group consisting of the following general formula (10).

When the structure of the above formula (14) is derived from a diamine compound used in the preparation of polyimide and polyimide precursor, it is preferably a structure selected from the group consisting of the following general formula (11).

The structure of the general formula (14) is not limited to the structures listed in (9) to (11) above. The above structures can be one or a combination of two or more.

From the viewpoints of resolution, moisture permeability and low dielectric loss tangent, (A) at least one resin selected from polyimide and polyimide precursor is preferably a structure represented by the following general formula (15).

{wherein, Rz each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom or form a ring structure, a represents an integer of 0 to 4, A each independently represents an oxygen atom or a sulfur atom, and B is a single bond or one of the following formulae: [Chemical 14]

The photosensitive resin composition of the present invention heats and hardens the photosensitive resin composition to obtain a cured polyimide film having an amide group concentration U of 12 wt% to 26 wt%. In the specification of the present invention, "amide group concentration U" refers to the ratio of the molecular weight of the amide group to the molecular weight of the repeating unit having a structure derived from tetracarboxylic dianhydride and a diamine compound in the cured polyimide film obtained by heating and hardening the photosensitive resin composition at 350°C. The reason for setting heating and curing at 350°C as a condition is to use the state where the polyimide precursor is almost 100% imidized as a standard to clarify the standard of aliphatic hydrocarbon concentration T. It is not intended to heat and cure the photosensitive resin composition at 350°C in actual use.

If the imide group concentration U is 12.0wt% or more, the embossed pattern tends to have a good resolution. The imide group concentration U is preferably 12.5wt% or more, and more preferably 13.5wt% or more. On the other hand, by making the imide group concentration U less than 26wt%, the dielectric loss tangent of the obtained polyimide cured film tends to be good. The imide group concentration U is more preferably 23.0wt% or less, and further preferably 21.0wt% or less.

The imide group concentration U in the repeating unit of the polyimide cured film is the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in preparing the polyimide precursor, and is represented by the following formula (I): 70.02×2/[Mw(A)+Mw(B)-36]×100 (I)

{In formula (I), Mw(A) represents the molecular weight of tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of diamine}. Furthermore, when two or more tetracarboxylic dianhydride and/or diamine compounds are used, for example, when two tetracarboxylic dianhydrides and/or diamines are used for preparation, it is represented by the following formula (II): 70.02×2/[Mw(A1)× _a1 +Mw(A2)× _a2 +Mw(B1)× _b1 +Mw(B2)× _b2-36 ]×100 (II)

{In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, _a1 represents the content of the first tetracarboxylic dianhydride, _a2 represents the content of the second tetracarboxylic dianhydride, Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, _b1 represents the content of the first diamine compound, and _b2 represents the content of the second diamine compound; wherein _a1 , _a2 , _b1 , and _b2 satisfy _a1 + _a2 =1 and _b1 + _b2 =1, respectively}. When three or more tetracarboxylic dianhydrides and/or diamines are used, the same method is used to obtain the value. When tetracarboxylic acids and/or tetracarboxylic acid chlorides are used as raw materials, the corresponding mass of tetracarboxylic dianhydrides is used for calculation.

The polyimide and/or polyimide precursor resin may also have at least one terminal structure selected from the group consisting of the following general formulas (1) to (3).

[Chemistry 15]

{W is a 2-3 valent organic group, R ₁ to R ₃ are independently a hydrogen atom or a univalent organic group with 1 to 3 carbon atoms, m ₁ is an integer of 1 to 2, m ₂ is an integer of 2 to 10, and * means bonding to the main chain of the resin}. By making the polyimide and/or polyimide precursor have such a terminal structure, a negative photosensitive resin composition with low dielectric properties, low moisture permeability, good chemical resistance and high resolution can be obtained.

The structure of W is not particularly limited, but is preferably a 2-3 valent organic group with a weight average molecular weight of less than 300, more preferably a 2-3 valent organic group with 1-5 carbon atoms, and even more preferably a 2-3 valent organic group with 1-3 carbon atoms.

The (A) polyimide precursor may also have a polymerizable group at the end of the main chain. The (A) polyimide precursor having a polymerizable group preferably has a structure represented by the following general formula.

{In formula (E1), _a1 includes at least one of an amide bond, an imide bond, a urea bond, and a urethane bond, _b1 is a reactive substituent crosslinked by heat or light, e1 is a monovalent organic group having ₁ to 30 carbon atoms, _R19 and _R22 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, _R20 and _R21 are each independently a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or a portion of an aromatic ring or an aliphatic ring; wherein _R20 and _R21 are not both hydrogen atoms}.

(In the formula, _f1 includes at least one of an amide bond, an imide bond, a urea bond, a urethane bond, and an ester bond; _g1 is a reactive substituent that is crosslinked by heat or light; _R23 to _R27 are independently a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or together form an aromatic ring or an aliphatic ring; wherein _R24 , _R25 , and _R26 will not be hydrogen atoms at the same time). By providing the polyimide precursor with a polymerizable group at such a terminal, a negative photosensitive resin composition having low dielectric properties, low moisture permeability, good chemical resistance, and high resolution can be obtained.

_f1 is preferably at least one group including an amide group, an imide bond, a urea group, and a carbamate group. When _f1 is an ester group, it is easily hydrolyzed and thus may not crosslink. These four groups (amide group, imide bond, urea group, and carbamate group) are difficult to be hydrolyzed and thus have higher chemical resistance.

The reactive substituent _b1 crosslinked by heat or light is preferably at least one selected from acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxide, cyclobutyl, carbonate, hydroxyl, oxadienyl, hydroxymethyl, and alkoxyalkyl. From the viewpoint of film thickness uniformity, _b1 is preferably at least one selected from acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, and ethynyl. Methacryl is particularly preferred.

The reactive substituent _g1 crosslinked by heat or light is, for example, at least one selected from acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxide, cyclobutylene, carbonate, hydroxyl, oxadienyl, hydroxymethyl, and alkoxyalkyl. From the viewpoint of film thickness uniformity, _{g1 is preferably at least one selected from acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, and ethynyl. More preferably, g1 is} methacryl.

The following are specific examples of compounds having a reactive substituent that reacts with heat or light and having a site that also reacts with a carboxyl group, and the main chain terminal of a polyimide precursor modified with a reactive substituent.

The aliphatic hydrocarbon concentration T of the polyimide cured film obtained by heating and curing the photosensitive resin composition is preferably 4wt% to 35wt%. In the specification of this case, "aliphatic hydrocarbon concentration T" refers to the ratio of the total molecular weight of aliphatic hydrocarbons in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C to the molecular weight of the repeating units including tetracarboxylic dianhydride and diamine compound. The reason for heating and curing at 350°C as a standard is that by taking the state of almost 100% imidization of the polyimide precursor as a standard, it is easy to adjust the aliphatic hydrocarbon concentration T, and it is not intended to heat and cure the photosensitive resin composition at 350°C in actual use. Here, "aliphatic hydrocarbon" is a hydrocarbon group branched from the main chain of the polyimide precursor, which does not contain a heteroatom and has at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure, and can be either a straight chain or a branched chain. The part of the alkylene skeleton that constitutes part of the main chain and the quaternary carbon (carbon that is substituted with two and constitutes part of the main chain) that constitutes part of the main chain are not included in the "aliphatic hydrocarbons" in the calculation of the aliphatic hydrocarbon concentration. The aliphatic hydrocarbons that constitute the side chain branching from the main chain may be saturated or unsaturated, and may be chain or alicyclic, and are included in the "aliphatic hydrocarbons" in the calculation of the aliphatic hydrocarbon concentration. As examples of the structure of the "aliphatic hydrocarbon", there are the structures represented by the following general formula (A1), the following general formula (A2), and the following general formula (A3).

In the general formulas (A1) to (A3), L is a single bond or an a-valent organic group which may be a linear or branched saturated hydrocarbon group or a linear or branched unsaturated hydrocarbon group, b is an integer of 1 to 6, and R _a1 is an organic group having 1 to 8 carbon atoms or a hydrogen atom which may have a ring structure. * is a linking group to the main chain structure.

From the viewpoint of the dielectric loss tangent of the polyimide cured film, the aliphatic hydrocarbon group is preferably a monovalent aliphatic saturated hydrocarbon group having 1 to 3 carbon atoms, for example, a methyl group. If the aliphatic hydrocarbon group concentration T is 4wt% or more, the dielectric loss tangent of the polyimide cured film tends to be good. The aliphatic hydrocarbon group concentration T is preferably 5wt% or more, more preferably 7wt% or more, and further preferably 8wt% or more. By making the aliphatic hydrocarbon group concentration T 5wt% or more, there is a tendency for good moisture permeability. On the other hand, by making the aliphatic hydrocarbon group concentration T 35wt% or less, the resolution and moisture permeability of the obtained polyimide cured film tend to be good. The aliphatic hydrocarbon concentration T is preferably below 28wt%, more preferably below 17wt%, and further preferably below 12%.

The aliphatic hydrocarbon concentration T is the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the polyamide and/or polyimide precursor, and is represented by the following formula (I): [Mw(P)+Mw(Q)]/[Mw(A)+Mw(B)-36]×100 (I)

{In formula (I), Mw(P) represents the sum of the molecular weights of aliphatic hydrocarbon groups in tetracarboxylic dianhydride, Mw(Q) represents the sum of the molecular weights of aliphatic hydrocarbon groups in diamine compounds, Mw(A) represents the molecular weight of tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of diamine compounds}.

When two or more tetracarboxylic dianhydrides and/or diamine compounds are used, for example, when two tetracarboxylic dianhydrides and two diamine compounds are used, it is represented by the following formula (II): [Mw(P1)× _a1 +Mw(P2)× _a2 +Mw(Q1)× _b1 +Mw(Q2)× _b2 ]/[Mw(A1)× _a1 +Mw(A2)× _a2 +Mw(B1)× _b1 +Mw(B2)× _b2-36 ]×100 (II)

{In formula (II), Mw(P1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, Mw(P2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second tetracarboxylic dianhydride, Mw(Q1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first diamine compound, and Mw(Q2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second diamine compound; Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, _a1 represents the content ratio of the first tetracarboxylic dianhydride, and _a2 represents the content ratio of the second tetracarboxylic dianhydride; Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, _b1 represents the content ratio of the first diamine compound, and _b2 represents the content ratio of the second diamine compound; and _a1 , _a2 , _b1 , and _b2 respectively satisfy _a1 +a2. _b2 =1, _b1 + _b2 =1}. When three or more tetracarboxylic dianhydrides and/or diamine compounds are used, the molecular weight is calculated in the same manner. When tetracarboxylic acid and/or tetracarboxylic acid chloride is used as the raw material, the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.

It is preferred that at least one of the tetracarboxylic dianhydride and the diamine compound has an aliphatic hydrocarbon group. When the diamine compound has an aliphatic hydrocarbon group, the moisture permeability tends to decrease, so it is preferred. When both the diamine compound and the tetracarboxylic dianhydride have an aliphatic hydrocarbon group, the solubility in the developer tends to increase, thereby increasing the developing speed, so it is preferred.

In the IR spectrum of a polyimide obtained by heating and curing the polyimide precursor (A) at 230°C, the maximum peak intensity of the absorption peak in the range of 1450 cm ^-1 to 1550 cm ^-1 is defined as Ph ₁ , the peak intensity of the second intensity is defined as Ph ₂ , and the peak intensity near 1380 cm ^-1 is defined as Im ₁ . When Ph ₁ is normalized to 1, the following formula (2) is preferably satisfied: 0.34≦Ph ₂ ×Im ₁ ≦1.2 (2).

The measurement conditions of the IR spectrum are carried out using the method described in the following embodiment. The peak intensity of the low-wavelength side and the high-wavelength side of the peak top is lower than the peak intensity of the peak top, and the peak intensity of the low-wavelength side and the high-wavelength side is higher than the peak intensity of the peak top. It is not considered a peak.

For example, in the case of polyimide having the IR spectrum shown in the graph of Fig. 1 , Ph ₁ =1 (1500 cm ^-1 ), Ph ₂ =0.42 (1473 cm ^-1 ), and Im ₁ =0.68 (1373 cm ^-1 ). The signal appearing on the high-frequency side of Ph ₁ (1512 cm ^-1 ) does not appear as a peak.

When there is only one peak in the range of 1450 cm ^-1 to 1550 cm ^-1 , Ph ₂ is set to 0. The peak intensity near 1380 cm ^-1 is the value of the maximum peak in the range of ±10 cm ^-1 of each wave number.

Ph ₂ × Im ₁ is preferably 0.34 or more, more preferably 0.36 or more, and more preferably 0.40 or more. When it is 0.45 or more, the resolution tends to be good. Although it is not limited in theory, it is considered that by making Ph ₂ × Im ₁ 0.34 or more, the solubility of the polyimide precursor is improved, and the resolution becomes good. On the other hand, Ph ₂ × Im ₁ is preferably 1.2 or less. When it is 1.1 or less, the dielectric loss tangent tends to be good. Although it is not limited in theory, it is considered that by making Ph ₂ × Im ₁ 1.2 or less, the molecular motion in the high-frequency region is reduced.

In the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, it is preferred to satisfy the following formula (1): -12.6<U-T<16.0 (1)

{wherein, U represents the imide group concentration of the polyimide, and T represents the aliphatic hydrocarbon group concentration of the polyimide}. U-T is preferably -12.6 or more, more preferably -11.0 or more, and when it is -10 or more, there is a tendency for better resolution. U-T is preferably 16.0 or less, more preferably 12.5 or less, and more preferably 12.0 or less, and when it is 11.0 or less, there is a tendency for excellent moisture permeability. The reason for using heating and curing at 350°C as a standard is that the aliphatic hydrocarbon concentration T can be easily adjusted by using the state where the polyimide precursor is almost 100% imidized as a standard, and it is not intended to heat and cure the photosensitive resin composition at 350°C in actual use.

As the (A) polyimide precursor, there can be exemplified a polyimide precursor having a structural unit represented by the following general formula (4).

{wherein, _X1 is a tetravalent organic group having 6 to 40 carbon atoms, _Y1 is a divalent organic group having 6 to 40 carbon atoms, _n1 is an integer of 2 to 150, _R4 and _R5 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R4 and _R5 is a group represented by the following general formula (5)}.

{wherein, R ₆ , R ₇ and R ₈ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10}. Furthermore, R ₄ and R ₅ in the general formula (4) are also referred to as a side chain or a side chain structure of a polyimide precursor. R ₆ in the general formula (5) is preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitivity, R ₇ and R ₈ are preferably a hydrogen atom. Furthermore, from the viewpoint of photosensitivity, m ₂ is an integer of 2 to 10, preferably an integer of 2 to 4.

From the viewpoint of resolution and low dielectric properties, the ratio of photosensitive groups in each repeating unit in the (A) polyimide precursor resin represented by the general formula (4) is preferably 15wt%~35wt%. From the viewpoint of dielectric properties, it is better to have fewer photosensitive groups, and from the viewpoint of resolution, it is better to have more photosensitive groups. In the specification of this case, "ratio of photosensitive groups" means the ratio of the molecular weight of the compound containing photopolymerizable groups constituting the repeating unit represented by the general formula (4) as a reference. As a photopolymerizable group, for example, an unsaturated double bond can be cited.

The ratio of the photosensitive groups of each repeating unit of the polyimide precursor resin is the molecular weight of the tetracarboxylic dianhydride and diamine compound used in the preparation of the polyimide precursor, and is represented by the following formula (I): [Mw(R)]/[Mw(A)+Mw(B)+Mw(R)-36]×100 (I)

{In formula (I), Mw(R) represents the sum of the molecular weights of the photopolymerizable group-containing compound (photopolymerizable group-containing compound), Mw(A) represents the molecular weight of tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound}.

Furthermore, when two or more tetracarboxylic dianhydrides and/or diamine compounds are used, the concentration T of aliphatic hydrocarbons is calculated based on the ratio of the raw materials in the same manner as the above definition.

In the case of a copolymer of a compound containing a photopolymerizable group and a compound not containing a photopolymerizable group, it is represented by the following formula (II): [Mw(R)×c ₁ ]/[Mw(A)+Mw(B)+Mw(R)×c ₁ +Mw(S)×c ₂ -36]×100 (II)

{In formula (II), Mw(R) represents the sum of the molecular weights of the compounds containing a photopolymerizable group, Mw(S) represents the sum of the molecular weights of the compounds not containing a photopolymerizable group, Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound; _c1 represents the content of the compounds containing a photopolymerizable group, _c2 represents the content of the compounds not containing a photopolymerizable group, and _c1 and _c2 respectively satisfy _c1 + _c2 =1}. When tetracarboxylic acid and/or tetracarboxylic acid chloride are used as the raw materials, the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.

From the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition, _n1 in the general formula (4) is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

In the above general formula (4), in terms of both heat resistance and photosensitivity, the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group or alicyclic aliphatic group in which _-COOR1 and _-COOR2 are adjacent to -CONH-. As the tetravalent organic group represented by _X1 , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, having the following general formula (7):

{In formula (7), R ₁₁ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, and a C1-C10 fluorine-containing alkyl group, m ₅ is an integer of 0-2, m ₆ is an integer of 0-3, and m ₇ is an integer of 0-4}, but is not limited thereto. In addition, the structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula (7) is particularly preferred in terms of both heat resistance and photosensitivity.

In the above general formula (4), in terms of both heat resistance and photosensitivity, the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms, for example, the following general formula (8):

{In formula (8), R ₁₁ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, and a C1-C10 fluorine-containing alkyl group, m ₅ is an integer of 0-2, m ₆ is an integer of 0-3, and m ₇ is an integer of 0-4}, but is not limited thereto. In addition, the structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formula (8) is particularly preferred in terms of both heat resistance and photosensitivity.

In the polyimide precursor (A), at least one of _X1 as a skeleton component derived from a tetracarboxylic acid compound or _Y1 as a skeleton component derived from a diamine compound preferably has a structure in which two or more benzene rings are bonded. The number of benzene rings may be 3 or more, 4 or more, 6 or less, 5 or less, or 4 or less, and more preferably 4. By making the polyimide precursor (A) have such a structure, the resolution of the negative photosensitive resin composition is maintained, and the obtained hardened relief pattern tends to have low dielectric properties.

In the general formula (4), the divalent organic group represented by _Y1 preferably has a structure of the general formula (14). When the structure of the general formula (14) is included in _Y1 in the general formula (4), the resolution tends to be excellent. Although not limited in theory, it is believed that the electron density of the aromatic ring increases, the CT migration is promoted, and thus the expansion of the film during development is suppressed.

[(A) Preparation method of polyimide precursor]

The ester bond type polyimide precursor having at least one terminal structure selected from the group consisting of the above general formulas (1) to (3) can be obtained by any of the following methods. For example, it can be obtained by first synthesizing an esterified tetracarboxylic dianhydride having a terminal structure, and then subjecting it to amide condensation with a diamine compound.

(Introduction method of terminal structure 1)

When forming the terminal structures of the above general formula (1) and the above general formula (2), the tetracarboxylic dianhydride having the desired tetravalent organic group X is reacted with a compound having an isocyanate group, and then an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) is reacted to prepare a tetracarboxylic acid (hereinafter also referred to as an acid/ester/imide) that is partially imidized or imide-derivatized (derived from the structure of the above general formula (2))/esterified. In order to promote the reaction of the tetracarboxylic dianhydride with the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. can be used. The above-mentioned alcohol having a photopolymerizable group can also be used in combination with a saturated aliphatic alcohol.

(Introduction method of terminal structure 2)

When forming the terminal structure of the above general formula (3), the tetracarboxylic dianhydride having the desired tetravalent organic group X is reacted with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester body), and then a compound having an isocyanate group is reacted to prepare a partially esterified/amidated tetracarboxylic acid (hereinafter, also referred to as an acid/ester/amide body). In order to promote the reaction of the tetracarboxylic dianhydride with the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. can be used. The above-mentioned alcohol having a photopolymerizable group can also be used in combination with a saturated aliphatic alcohol.

(Preparation of acid/ester)

As the tetracarboxylic dianhydride having a tetravalent organic group _X1 with a carbon number of 6 to 40 which can be preferably used for preparing the ester bond type polyimide precursor, in addition to the tetracarboxylic dianhydride derived from the structure exemplified above, for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3 ',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride, etc., but not limited to them. Moreover, these can be used alone or in combination of two or more.

The tetracarboxylic dianhydride containing a tetravalent organic group _X1 having 6 to 40 carbon atoms is used, and the terminal structure is formed by the above-mentioned introduction method 1 or introduction method 2. The order of the reaction varies depending on the introduction method.

Examples of the photopolymerizable compound preferably used for synthesizing the esterified tetracarboxylic acid having a reactive terminal represented by the general formula (1) to (3) include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(diacryloyloxymethyl)ethyl isocyanate. Examples of the alcohol having a photopolymerizable group include 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-butoxypropyl acrylate ...methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy- -3-cyclohexyloxypropyl ester, 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, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

As the above-mentioned alcohols having a photopolymerizable group, as saturated aliphatic alcohols that can be used arbitrarily, saturated aliphatic alcohols with 1 to 4 carbon atoms are preferred. Specific examples thereof include: methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc.

The above tetracarboxylic dianhydride and alcohol are preferably stirred and mixed in the presence of an alkaline catalyst such as pyridine and preferably in an appropriate reaction solvent at a temperature of 20-50°C for 4-10 hours to perform an esterification reaction of the anhydride to obtain the desired acid/ester.

As the above-mentioned reaction solvent, it is preferred that the raw materials of tetracarboxylic dianhydride and alcohols, and the acid/ester body as the product are completely dissolved. It is more preferred that the polyimide precursor which is the amide condensation product of the acid/ester body and diamine is also completely dissolved in the solvent. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. As specific examples of these, 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. Examples of lactones include γ-butyrolactone, etc. Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc. Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc. Examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene, etc. These can be used alone or in combination of two or more as needed.

(Preparation of polyimide precursor)

An appropriate dehydrating condensing agent is added to the above acid/ester (typically in the form of a solution dissolved in the above reaction solvent) preferably under ice cooling to convert the acid/ester into a polyanhydride. Then, a diamine having a divalent organic group _Y1 with 6 to 40 carbon atoms dissolved or dispersed in a solvent is added dropwise thereto to allow the two to undergo amide condensation, thereby obtaining the target polyimide precursor. Diaminosiloxanes may also be used in combination with the above diamine having a divalent organic group _Y1 . Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. In the above manner, a polyanhydride compound as an intermediate is obtained.

Examples of diamines having a divalent organic group _Y1 having 6 to 40 carbon atoms that can be preferably used for the reaction with the polyanhydride compound obtained in the above manner include, in addition to diamines having the structures listed above, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminodiphenyl sulfone, 3'-Diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4- 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-aminophenyl) [0043] In the present invention, the present invention relates to diamines such as hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine sulfonate, 9,9-bis(4-aminophenyl)fluorene, bis{4-(4-aminophenoxy)phenyl}ketone, and compounds wherein a portion of the hydrogen atoms on the benzene rings are substituted with alkyl chains such as methyl and ethyl, 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 diamines are not limited to the diamines. The diamines may be used alone or in combination of two or more.

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 when preparing (A) the polyimide precursor.

As a method for introducing a reactive substituent that reacts with heat or light at the end of the main chain, the following method can be cited. First, during the condensation of amide, for example, diamine is added in excess, thereby making both ends of the main chain amino groups. Next, a compound having a reactive substituent that reacts with heat or light and having a site that also reacts with the amino group is reacted with the amino group. At this time, as the site that reacts with the amino group, examples include: acid anhydride, epoxy, isocyanate, etc. In addition, the following method can also be cited. First, during the condensation of amide, partially esterified tetracarboxylic acid is added in excess, thereby making both ends of the main chain carboxyl groups. Next, a compound having a reactive substituent that reacts with heat or light and having a site that also reacts with the carboxyl group is reacted with the carboxyl group. In this case, examples of the site that reacts with the carboxyl group include amines, alcohols, etc. Furthermore, as another synthesis method, the following method can be cited: first, an esterified tetracarboxylic acid having a terminal structure is synthesized, and then it is polycondensed with a diamine amide to obtain it. For example, the following methods can be cited: a method in which a tetracarboxylic acid dianhydride having a desired tetravalent organic group _X1 is reacted with a compound having an isocyanate group, and then reacted with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester); or a method in which a tetracarboxylic acid dianhydride having a desired tetravalent organic group _X1 is reacted with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester), and then reacted with a compound having an isocyanate group to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester). Saturated aliphatic alcohols can also be used in combination with the above-mentioned alcohols having a photopolymerizable group.

烯-2,3-二羧酸酐、伊康酸酐、甲基丙烯酸酐、甲基丙烯酸2-異氰酸基乙酯、丙烯酸2-異氰酸基乙酯、4-乙炔基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、二碳酸二-第三丁酯等。作為具有利用熱或光而反應之反應性取代基且具有亦會與羧基反應之部位之化合物，例如可例舉4-胺基苯乙烯、4-乙炔基苯胺等。 Examples of compounds having a reactive substituent that reacts with heat or light and having a site that also reacts with an amine group and are used to introduce a reactive substituent that reacts with heat or light into the terminal of the main chain include maleic anhydride, 5-nitropropene,

Examples of the compound having a reactive substituent that reacts with heat or light and having a site that also reacts with a carboxyl group include 4-aminostyrene and 4-ethynylaniline.

After the amide polycondensation reaction is completed, the water-absorbing byproducts of the dehydration condensation agent coexisting in the reaction solution are 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 polymer is repeatedly re-dissolved and re-precipitated as needed to purify the polymer and then 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.

From the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment, when measured by weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC), the weight average molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000. If the weight average molecular weight is 8,000 or more, the mechanical properties are good, and thus 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, and thus it is preferred. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained based on a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[(B) Photopolymerization initiator]

唑化合物；2,4,6-三甲基苯甲醯基-二苯基-氧化膦等氧化膦化合物，但並不限定於該等。上述所說明之(C)聚合起始劑亦可單獨或將2種以上混合使用。上述光聚合起始劑之中，尤其是就解像性之觀點而言，更佳為肟酯化合物。該等之中，尤佳為自由基種源自甲基。 (B) Photopolymerization initiators are compounds that can generate free radicals by active light to polymerize compounds containing ethylenically unsaturated groups. Examples of initiators that generate free radicals by active light include benzophenone, N-alkylaminoacetophenone, oxime esters, acridine, and compounds containing structures such as 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-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, propylene diphenyl Aromatic ketones such as methyl ketone, 4-benzoyl-4'-methyl diphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin; 1,2-octanedione, 1-[4-(phenylthio)-, 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) (Jiuzhou Strong Electronic 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) TR-PBG-326, product name) 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, but not limited to them. The above-mentioned (C) polymerization initiator can also be used alone or in combination of two or more. Among the above-mentioned photopolymerization initiators, oxime ester compounds are more preferred from the viewpoint of resolution. Among them, free radical species derived from methyl groups are particularly preferred.

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

[(C)Solvent]

(C) The solvent is not limited, as long as it can evenly dissolve or suspend (A) the polyimide precursor and (B) the photopolymerization initiator. Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofuran methyl alcohol, 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, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

According to the required coating film thickness and viscosity of the photosensitive resin composition, the above solvent can be used in a range of, for example, 30 to 1500 parts by mass, preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor. When the solvent contains an alcohol without an olefinic double bond, the content of the alcohol without an olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the alcohol without olefinic double bonds is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good, and when it is 50% by mass or less, the solubility of the (A) polyimide precursor becomes good.

[(D) Silane coupling agent]

In order to improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain (D) a silane coupling agent. (D) The silane coupling agent preferably has a structure represented by the following general formula (12).

{wherein, R ₁₂ is at least one selected from the group consisting of an epoxy group, a phenylamine group, a urea group, an isocyanurate group, and an ureido group, R ₁₃ is independently an alkyl group having 1 to 4 carbon atoms, R ₁₄ is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, d is an integer of 1 to 3, and m ₈ is an integer of 1 to 6}.

In general formula (12), d is not limited and may be an integer of 1 to 3. From the viewpoint of adhesion to the metal redistribution layer, it is preferably 2 or 3, and more preferably 3. _m8 is not limited and may be an integer of 1 to 6. From the viewpoint of adhesion to the metal redistribution layer, it is preferably 1 to 4. From the viewpoint of developability, it is preferably 2 to 5.

R ₁₂ is not limited, as long as it is a substituent containing any structure selected from the group consisting of an epoxy group, a phenylamino group, a urea group, an isocyanuric acid group, and an ureido group. Among them, from the viewpoint of developing properties and the adhesion of the metal redistribution layer, it is preferably at least one selected from the group consisting of a substituent containing a phenylamino group, a substituent containing a urea group, and a substituent containing an ureido group, and more preferably a substituent containing a phenylamino group. R ₁₃ is not limited, as long as it is an alkyl group having 1 to 4 carbon atoms. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. R ₁₄ is not limited, as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, the same alkyl group as R ₁₃ can be exemplified.

Examples of silane coupling agents containing epoxy groups include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glyceryloxypropylmethyldimethoxysilane, 3-glyceryloxypropyltrimethoxysilane, 3-glyceryloxypropylmethyldiethoxysilane, and 3-glyceryloxypropyltriethoxysilane. Examples of silane coupling agents containing phenylamine groups include N-phenyl-3-aminopropyltrimethoxysilane. Examples of silane coupling agents containing ureido groups include 3-ureidopropyltrialkoxysilane. Examples of silane coupling agents containing isocyanate groups include 3-isocyanatepropyltriethoxysilane.

[(E) Radical polymerizable compounds]

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

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

The amount of the compound having ethylenically unsaturated double bonds is 0.5 to 15 parts by mass relative to 100 parts by mass of (A) polyimide precursor.

[(F) Thermal crosslinking agent]

In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain (F) a thermal crosslinking agent.

(F) Thermal crosslinking agent refers to a compound that undergoes addition reaction or condensation polymerization reaction by heat. Such reactions can be carried out in combination with (A) resin and (F) thermal crosslinking agent, (F) thermal crosslinking agents with each other, and (F) thermal crosslinking agent and other components listed below. The reaction temperature is preferably above 150°C.

It is preferred that the (F) thermal crosslinking agent contains nitrogen atoms. This improves the interaction with the polyimide resin and can achieve higher chemical resistance. Examples of the (F) thermal crosslinking agent include: alkoxymethyl compounds, epoxy compounds, cyclohexane compounds, dimaleimide compounds, allyl compounds, and blocked isocyanate compounds.

As examples of alkoxymethyl compounds, the following compounds can be cited, but are not limited thereto.

[Chemistry 25]

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, diphenolic acid bis(3-ethyl-3-cyclohexanebutylmethyl)ether, methyl) ester, trihydroxymethylpropane tris(3-ethyl-3-oxocyclobutyl methyl) ether, pentaerythritol tetra(3-ethyl-3-oxocyclobutyl methyl) ether, poly[[3-[(3-ethyl-3-oxocyclobutyl)methoxy]propyl]silsesquioxane] derivative, oxocyclobutyl silicate, phenol novolac type oxocyclobutane, 1,3-bis[(3-ethyloxocyclobutane-3-yl)methoxy]benzene, OXT121 (Toagosei, trade name), OXT221 (Toagosei, trade name), etc. Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N '-1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane or 2,2-bis[4-(4-maleimidophenoxy)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 Chemicals 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 7961 manufactured by Mitsui Chemicals Co., Ltd., B-830, etc.), 4,4'-diphenylmethane diisocyanate 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-blocked isocyanates (e.g. Takenate B-846N manufactured by Mitsui Chemicals, Coronate BI-301, 2507, and 2554 manufactured by Tosoh, etc.), isophorone diisocyanate-blocked isocyanates (e.g. 7950, 7951, and 7990 manufactured by Baxenden, etc.). Among them, blocked isocyanate or dimaleimide compounds are preferred from the viewpoint of storage stability. (F) The thermal crosslinking agent may be used alone or in combination of two or more.

Based on the total mass of the solid components of the resin composition, the content of the (F) thermal crosslinking agent in the resin composition is 0.2 mass% to 40 mass%. From the perspective of low dielectric properties and chemical resistance, it is preferably 1 mass% to 20 mass%, and more preferably 2 mass% to 10 mass%.

[(G) Filler]

In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain (G) fillers. The fillers are not limited, as long as they are inert substances added to improve strength and various properties.

From the perspective of suppressing the increase in viscosity when making a resin composition, the filler is preferably in a particle shape. Examples of particle shapes include needle-shaped, plate-shaped, and spherical shapes, but from the perspective of suppressing the increase in viscosity when making a resin composition, the filler is preferably in a spherical shape.

Examples of needle-shaped fillers include: wollastonite, potassium titanate, hard silica, aluminum borate, needle-shaped calcium carbonate, etc.

Examples of plate-like fillers include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, plate-like calcium carbonate, etc.

As spherical fillers, there can be cited: calcium carbonate, silicon dioxide, aluminum oxide, titanium oxide, clay, magnesium aluminum carbonate, magnesium hydroxide, zinc oxide, barium titanate, etc. Among them, from the perspective of electrical properties and storage stability when making a resin composition, silicon dioxide, aluminum oxide, titanium oxide, and barium titanate are preferred, and silicon dioxide and aluminum oxide are more preferred.

The size of the filler is defined by the primary particle diameter in the case of spheres and by the length of the long side in the case of plates or needles. It is preferably 5nm~1000nm, and more preferably 10nm~1000nm. If it is 10nm or more, it tends to be sufficiently uniform when the resin composition is made. If it is 1000nm or less, it can be given photosensitivity. From the perspective of giving photosensitivity, it is preferably 800nm or less, more preferably 600nm or less, and particularly preferably 300nm or less. From the perspective of adhesion and uniformity of the resin composition, it is preferably 15nm or more, more preferably 30nm or more, and particularly preferably 50nm or more.

Based on the mass of the resin composition, the content of the (G) filler in the resin composition is 1vol%~20vol%, preferably 5vol%~20vol% from the perspective of dielectric properties, and more preferably 5vol%~10vol% from the perspective of resolution.

[Other ingredients]

The photosensitive resin composition may further contain components other than the above-mentioned (A) to (G) components. As other components, for example: (A) resin components other than polyimide precursors; organic compounds containing metal elements, sensitizers, thermal polymerization inhibitors, azole compounds, and hindered phenol compounds, etc.

唑、聚

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

Azoles, poly

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

The photosensitive resin composition may also contain an organic compound containing a metal element. The organic compound containing a metal element preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. Preferably, the organic group contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. By containing an organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases. As an organic titanium or zirconium compound 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.

Specific examples of organic titanium or zirconium compounds are shown in the following I)~VII):

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

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

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

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

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

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

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

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

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

The photosensitive resin composition can increase the imidization rate of the polyimide precursor contained in the resin composition by containing the above-mentioned organic compound containing metal elements, and can reduce the dielectric loss tangent of the cured film using the resin composition. Although not bound by theory, it is believed that the reason for increasing the imidization rate of the polyimide precursor is that the metal element contained in the organic compound containing metal elements coordinates to the carbonyl group derived from the ester group and/or carboxyl group of the polyimide precursor, thereby reducing the electron density of the carbon atom of the carbonyl group and promoting the ring closing reaction.

唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯等。該等可單獨或以複數種(例如2~5種)之組合使用。相對於(A)聚醯亞胺前驅物100質量份，增感劑之調配量較佳為0.1質量份~25質量份。 In order to improve the sensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of the sensitizer include: michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4, 4'-Bis(diethylamino)chalcone, p-dimethylaminocinnamylene, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethyl Aminocumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-butylbenzimidazole, 1-phenyl-5-butyltetrazole, 2-butylbenzothiazole, 2-(p-dimethylaminostyryl)benzo

azole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminophenylvinyl)styrene, etc. These can be used alone or in combination of multiple types (e.g., 2 to 5 types). The amount of the sensitizer is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of the polyimide precursor (A).

、N-苯基萘基胺、乙二胺四乙酸、1,2-環己烷二胺四乙酸、二醇醚二胺四乙酸、2,6-二-第三丁基-對甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺丙基胺基)苯酚、N-亞硝基-N-苯基羥基胺銨鹽、N-亞硝基-N(1-萘基)羥基胺銨鹽等。又，該等熱聚合抑制劑可使用1種，亦可以2種以上之混合物使用。作為熱聚合抑制劑之調配量，相對於(A)聚醯亞胺前驅物100質量份，較佳為0.005質量份~12質量份之範圍。 In order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, especially when stored in a solution state containing a solvent, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butyl o-cyclopentylphenol, phenanthridine,

, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. In addition, the thermal polymerization inhibitors can 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 relative to 100 parts by weight of the polyimide precursor (A).

In the case of using a substrate comprising copper or a copper alloy, 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. Moreover, these azole compounds may be used alone or as a mixture of two or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

-2,4,6-(1H,3H,5H)-三酮。 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 hindered phenol compounds 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-tetra[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tri

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Polyimide hardened film and its manufacturing method>

The present invention also provides a method for producing a polyimide cured film, which comprises the step of converting a photosensitive resin composition into polyimide. The method for producing a polyimide cured film of the present invention comprises, for example, the following steps (1) to (5): (1) coating the photosensitive resin composition of the present invention on a substrate to form a photosensitive resin layer on the substrate; (2) heating and drying the obtained photosensitive resin layer; (3) exposing the heated and dried photosensitive resin layer; (4) developing the exposed photosensitive resin layer; and (5) heating the developed photosensitive resin layer to form a polyimide cured film.

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

The specific steps in the method for manufacturing a hardened film can be performed according to steps (1) to (5) of the method for manufacturing a hardened film described above. The following describes the typical aspects of each step.

(1) Applying a photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate

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

(2) Heating and drying the obtained photosensitive resin layer

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

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

In this step, 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. The exposure can be performed through a photomask with a pattern or a main photomask (reticle), or can be performed directly. The light used for exposure is, for example, an ultraviolet light source, etc.

After exposure, in order to improve photosensitivity, etc., post-exposure baking (PEB) and/or pre-development baking can be performed at any temperature and time combination as needed. Regarding the range of baking conditions, the temperature is preferably 40~120℃, and the time is preferably 10 seconds~240 seconds, but it is not limited to this range, as long as it does not damage the various properties of the negative photosensitive resin composition of this embodiment.

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

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, a liquid coating method, and an immersion method accompanied by ultrasonic treatment. In addition, after development, in order to adjust the shape of the relief pattern, post-development baking can be performed at any combination of temperature and time as needed. As a developer for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. As a 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 a 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 bad solvent are mixed for use, it is preferred to adjust the ratio of the bad solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more, for example, several solvents may be used in combination. In the step of developing the exposed photosensitive resin layer, it is preferred to perform the above-mentioned coating-developing steps in a manner to obtain a photosensitive resin layer with a film thickness of 10 μm to 15 μm. The developing time is preferably 30 seconds or less, more preferably 25 seconds or less, and further preferably 20 seconds or less. Although there is no limit in theory, by keeping the development time below 30 seconds, a difference in solubility can be created between the exposed part and the exposed part, thereby creating a contrast and improving the resolution of the pattern.

(5) The step of heating the developed photosensitive resin layer to form a polyimide hardened film

In this step, the relief pattern obtained by the above-mentioned development is heated to disperse the photosensitive components, and the (A) polyimide precursor is imidized to convert it into a hardened relief pattern containing polyimide. As a method of heat curing, various methods can be selected, such as a method using a heating plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature program. Heating can be performed at 160°C to 400°C for 30 minutes to 5 hours. As an ambient gas during heat curing, air can be used, and inert gases such as nitrogen and argon can also be used. In the above manner, a hardened relief pattern (polyimide hardened film) can be manufactured.

The method for manufacturing the polyimide cured film of the present invention includes, for example, coating the photosensitive resin composition of the present invention on a substrate, performing exposure treatment, developing treatment, and then heating treatment. The dielectric loss tangent of the cured film is preferably 0.003 to 0.012 when measured at 40 GHz using the perturbation split cylindrical resonator method. Furthermore, the dielectric loss tangent can be measured using the perturbation split cylindrical resonator method shown in the following embodiment.

The present invention also provides a polyimide cured film obtained from the photosensitive resin composition described above. The moisture permeability of the cured film is preferably less than 800, and more preferably less than 700. From the perspective of dielectric loss tangent, the lower the moisture permeability, the smaller the frequency dependence of the dielectric loss tangent tends to be, so it is good, but on the other hand, from the perspective of resolution, the lower the moisture permeability, the worse the solubility of the unexposed part during patterning, and the worse the resolution, so it is more preferably 500 or more and less than 800. By less than 800, a cured film with higher reliability can be obtained. For details of the method for measuring the moisture permeability, refer to the following content. From the perspective of resolution, dielectric properties and the frequency dependence of dielectric loss tangent, it is preferred that the product of dielectric loss tangent and moisture permeability (tanδ ₄₀ ×WVTR) is within a certain fixed range. When the value of dielectric loss tangent at 40 GHz is used, it is preferred to satisfy the following equation (3): 3.0 < tanδ ₄₀ ×WVTR < 10.0 (3)

By making tanδ ₄₀ ×WVTR in the range of 3.0~10.0, a polyimide cured product with excellent resolution and dielectric properties and low frequency dependence can be obtained. The difference between the dielectric loss tangent at 40GHz and 10GHz is preferably less than 0.0015, and more preferably less than 0.001.

The substrate on which the hardened relief pattern produced by the present invention is formed is preferably formed on a substrate selected from the group consisting of resin, silicon (Si), copper (Cu), aluminum (Al) and combinations thereof, and is particularly preferably formed on Cu. When the hardened relief pattern is formed on Cu, it can also be formed on a Cu layer formed on a Si wafer. Other metal layers can also be formed between the Si wafer and the Cu layer. As the metal layer formed between the Si wafer and the Cu layer, a Ti layer is preferably used.

The vertical and horizontal ratio of the hardened embossed pattern is preferably 0.5 or more, more preferably 1.0 or more, and more preferably 1.5 or more. By making the vertical and horizontal ratios higher, finer wiring can be formed. Regarding the minimum opening size of the through hole, for example, in a hardened film formed with a thickness of 10μm, it is preferred to open a through hole of 20μm or less, more preferably to open a through hole of 15μm or less, and more preferably to open a through hole of 10μm or less.

<Semiconductor devices>

The present invention also provides a semiconductor device having a hardened relief pattern obtained by using the photosensitive resin composition of the present invention and by the above-mentioned method for manufacturing a hardened relief pattern. Therefore, a semiconductor device having 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 is provided. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-mentioned method for manufacturing a hardened relief pattern as a part of the steps. The semiconductor device can be manufactured by forming the hardened embossed pattern formed by the above-mentioned hardened embossed pattern manufacturing method as a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining it with a known semiconductor device manufacturing method.

The polyimide contained in the hardened relief pattern (polyimide hardened film) formed by the above-mentioned polyimide precursor composition preferably has a structure represented by the following general formula (13):

{In general formula (13), _X1 and _Y1 are the same as _X1 and _Y1 in the above general formula (4), and _n2 is an integer of 2 to 150}.

<Display device>

The present invention also provides a display device, which uses the photosensitive resin composition of the present invention, and has a display element and a cured film disposed on the upper part of the display element, and the cured film is the above-mentioned cured convex pattern. Here, the cured convex pattern can be directly laminated with the display element, or it can be laminated with other layers. For example, as the cured film, there can be cited: surface protection films, insulating films, and flattening films of TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-Domain Vertical Alignment) type liquid crystal display devices, and partitions for cathodes of organic EL (Electroluminescence) elements.

In addition to being applied to 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 coatings of flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[Implementation example]

The physical properties of the photosensitive resin compositions in the embodiments, comparative examples, and preparation examples of the present invention are measured and evaluated according to the following methods.

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

The weight average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (converted to standard polystyrene). The column used for 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 used was Shodex RI-930 manufactured by Showa Denko Co., Ltd.

(2) Resolution and development time of hardened relief patterns on Cu substrates

On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries Co., Ltd., thickness 625±25μm), a 200nm thick Ti and a 400nm thick Cu were sputter-plated in sequence using a sputtering device (model L-440S-FHL, manufactured by CANON ANELVA). Then, a photosensitive resin composition prepared by the following method was spin-coated on the wafer using a coating developer (model D-Spin60A, manufactured by SOKUDO), and dried on a heating plate at 110°C for 3 minutes to form a photosensitive resin layer with a thickness of about 13.5μm. Using a photomask with a test pattern, the photosensitive resin layer was irradiated with an energy of 200 mJ/ ^cm2 through a prism GHI (manufactured by ULTRA TECH) equipped with an i-ray filter. Then, the photosensitive resin layer was spray developed using a coating developer (model D-Spin60A, manufactured by SOKUDO) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The time of the spray development at this time was set as the development time. The wafer with the embossed pattern formed on Cu was heated for 2 hours at 230°C in a nitrogen atmosphere using a temperature-programmed curing furnace (model VF-2000, manufactured by Koyo Lindberg), thereby obtaining a hardened embossed pattern made of resin with a thickness of about 10 μm on Cu. The produced embossed pattern was observed under an optical microscope to determine the size of the minimum opening pattern of the through hole. At this time, if the area of the opening portion of the obtained pattern is more than 1/2 of the opening area of the corresponding pattern mask, it is considered to be resolved, and the resolution is determined based on the length of the mask opening edge corresponding to the resolved opening portion with the smallest area (the size of the opening pattern) and the following evaluation criteria.

(Evaluation criteria)

A: The minimum opening pattern size is less than 10μm

B: The minimum opening pattern size is greater than 10μm and less than 15μm

C: The minimum opening pattern size is greater than 15μm and less than 20μm

D: The minimum opening pattern size is 20μm or more

(3) Measurement of dielectric properties (dielectric constant: Dk, dielectric loss tangent: Df)

A 6-inch silicon wafer (Fujimi Electronics Industries Co., Ltd., thickness 625±25μm) was sputter-plated with aluminum (Al) to a thickness of 100nm using a sputter coating device (model L-440S-FHL, manufactured by CANON ANELVA) to prepare a sputter-plated Al wafer substrate. A photosensitive resin composition prepared by the following method was spin-coated on the sputter-plated Al wafer substrate using a spin coating device (model D-spin60A, manufactured by SOKUDO) and heated and dried at 110°C for 180 seconds to form a photosensitive resin layer with a thickness of about 13.5μm. After that, the whole surface was exposed to ghi line with an exposure amount of 600mJ/ ^cm2 using an alignment machine (PLA-501F, manufactured by Canon Inc.), and a heat curing treatment was performed at 230°C for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to form a cured film made of resin with a thickness of about 10μm on the Al wafer. The cured film was cut into 80mm long and 62mm wide (for 10GHz measurement) and 40mm long and 30mm wide (for 40GHz measurement) using a wafer dicing machine (manufactured by DISCO, model name DAD-2H/6T), and then immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer to produce a film sample. After drying the film sample in an oven at 50°C for 24 hours, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the film sample at 10 GHz and 40 GHz were measured using the resonance perturbation method. The details of the measurement method are as follows.

(Measurement method)

Disturbance method: Split cylindrical resonator method

(Device structure)

Network Analyzer:

PNA Network analyzer N5224B

(Made by KEYSIGHT)

Split cylindrical resonator:

CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 10GHz)

CR-740 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 40GHz)

(4) Moisture permeability test

A 6-inch silicon wafer (Fujimi Electronics Industries Co., Ltd., thickness 625±25μm) was sputter-plated with aluminum (Al) to a thickness of 100nm using a sputter coating device (model L-440S-FHL, manufactured by CANON ANELVA) to prepare a sputter-plated Al wafer substrate. A photosensitive resin composition prepared by the following method was spin-coated on the sputter-plated Al wafer substrate using a spin coating device (model D-spin60A, manufactured by SOKUDO) and heated and dried at 110°C for 180 seconds to form a photosensitive resin layer with a thickness of about 13.5μm. After that, the whole surface was exposed using a ghi line with an exposure amount of 600mJ/ ^cm2 using an alignment machine (PLA-501F, manufactured by Canon Inc.), and a heat curing treatment was performed at 230°C for 2 hours in a nitrogen atmosphere using a longitudinal curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to form a cured film made of resin with a thickness of about 10μm on the Al wafer. The cured film was cut into 80mm long and 62mm wide using a wafer dicing machine (manufactured by DISCO, model name DAD-2H/6T), immersed in a 10% hydrochloric acid aqueous solution, and then peeled off from the silicon wafer to prepare a film sample. The moisture permeability was measured according to the cup method of JIS Z 0208. Furthermore, the amount of calcium chloride used was 40 g and the moisture permeability conditions were 65°C/90%RH. The test was conducted for 24 hours, after which the sample was taken out of the thermostatic machine and placed at room temperature for 30 minutes, and the weight was measured. The water permeability (WVTR) was calculated according to the following formula.

WVTR = {(weight after test) - (weight before test)} / (0.03 ² × π) (Formula X)

{In formula X, 0.03 represents the radius of the cup (m)}

The WVTR mentioned here is the value for a 10um hardened film and is dependent on the film thickness. For example, when the film thickness is 20um, it becomes 1/2 of the WVTR value obtained at 10um. The lower the WVTR value, the lower the water vapor permeability of the film. In addition, there is a tendency that the higher the hydrophobicity of the film or the higher the density of the film, the lower the WVTR.

(5) IR measurement

IR measurement was performed on the film obtained in (3) above using Nicolet 380 and the ATR (Attenuated Total Reflectance) method by scanning 50 times in the range of 700 cm ^-1 to 4000 cm ^-1 . A silicon prism was used for the sample contact portion. The maximum peak intensity of the absorption peak in the range of 1450 cm ^-1 to 1550 cm ^-1 was set as Ph ₁ , the peak intensity of the second intensity was set as Ph ₂ , the peak intensity near 1380 cm ^-1 was set as Im ₁ , and Ph ₁ was normalized to 1 to calculate Ph ₂ and Im _1. Furthermore, the peak intensity near 1380 cm ^-1 was set as the largest peak within 1380 cm ^-1 ± 10 cm ^-1 .

[Manufacturing of diamine X-1]

A 5L four-necked flask was replaced with Ar, and 172.02g of 4,4'-butylindenebis(6-tert-butyl-m-cresol), 155.84g of 4-chloronitrobenzene, and 1.5L of DMF were added and stirred. _186.42g of _K2CO3 was added and heated at 150°C for 5 hours. The disappearance of the raw materials and the intermediates was confirmed by TLC (Thin Layer Chromatography ). After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure at 80°C. The concentrated residue was injected into 1.6L of ion exchange water, and 2.5L of ethyl acetate was added and the solution was purified by separation three times. The organic layer was recovered and dried by adding MgSO _4. After drying, the impurities were removed by filtration, 800 mL of toluene was added to dissolve it, and the obtained product was added to 4.0 L of methanol and stirred for 30 minutes. After stirring, the filtrate was filtered and recovered, and dried at 80°C for 12 hours. The obtained reactant after drying was put into a 5L four-necked flask replaced by Ar, and then 19.04 g of 5% Pd/C (EA) and 1.9 L of THF were added and stirred. The flask was heated to 40°C for H2 bubbling (10 mL/min), and the reduction reaction was carried out for 24 hours. The reaction solution was filtered through diatomaceous earth, and the eluted fraction of the target product was recovered by silica gel chromatography and concentrated under reduced pressure to obtain diamine X-1.

[(A) Production of polyimide precursors] Synthesis of polyimide precursor (polymer A-1):

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

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. Next, a suspension of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane suspended in 350 ml of γ-butyrolactone was added while stirring for 60 minutes. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst ^TM 15" manufactured by Organo Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdered polymer A-1. The weight average molecular weight (Mw) of the polymer A-1 was measured and the result was 21,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-1 was 19.6 wt%, and the aliphatic hydrocarbon group concentration T was 8.4 wt%. The "imide group concentration U" and "aliphatic hydrocarbon group concentration T" were calculated by converting the polyimide of the polyimide cured film obtained by heating and curing at 350°C (the same applies hereinafter).

Synthesis of polyimide precursor (polymer A-2):

In the synthesis of the above polymer A-1, 260.2 g of 4,4'-(4,4'-isopropyldiphenyloxy) dianhydride was used instead of 155.1 g of ODPA, and 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. In addition, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1 to obtain polymer A-2. The weight average molecular weight (Mw) of the polymer A-2 was measured and found to be 23,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-2 was 20.1 wt%, and the aliphatic hydrocarbon concentration T was 8.6 wt%.

Synthesis of polyimide precursor (polymer A-3):

In the synthesis of the above polymer A-1, 146.3 g of 1,4-bis(4-aminophenoxy)-2,3,5-trimethylbenzene was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-3. The weight average molecular weight (Mw) of the polymer A-3 was measured and found to be 20,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-3 was 23.0 wt%, and the aliphatic hydrocarbon concentration T was 7.4 wt%.

Synthesis of polyimide precursor (polymer A-4):

In the synthesis of the above polymer A-1, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of ODPA. In addition, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-4. The weight average molecular weight (Mw) of the polymer A-4 was measured and the result was 21,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-4 was 20.1 wt%, and the aliphatic hydrocarbon concentration T was 8.6 wt%.

Synthesis of polyimide precursor (polymer A-5):

In the synthesis of the above polymer A-1, 260.2 g of 4,4'-(4,4'-isopropyldiphenoxy) dianhydride was used instead of 155.1 g of ODPA. In addition, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-5. The weight average molecular weight (Mw) of the polymer A-5 was measured and the result was 24,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-5 was 15.2 wt%, and the aliphatic hydrocarbon concentration T was 9.8 wt%.

Synthesis of polyimide precursor (polymer A-6):

In the synthesis of the above polymer A-1, 260.2 g of 4,4'-(4,4'-isopropyldiphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 176.98 g of 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-6. The weight average molecular weight (Mw) of the polymer A-6 was measured and found to be 22,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-6 is 15.8wt%, and the aliphatic hydrocarbon concentration T is 16.2wt%.

Synthesis of polyimide precursor (polymer A-7):

In the synthesis of the above polymer A-1, 260.2 g of 4,4'-(4,4'-isopropyldiphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. In addition, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-7. The weight average molecular weight (Mw) of the polymer A-7 was measured and found to be 20,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-7 was 13.3 wt%, and the aliphatic hydrocarbon concentration T was 20.7 wt%.

Synthesis of polyimide precursor (polymer A-8):

In the synthesis of the above polymer A-1, 109.06 g of pyromellitic dianhydride was used instead of 150.1 g of ODPA, and 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. In addition, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-8. The weight average molecular weight (Mw) of the polymer A-8 was measured and found to be 14,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-8 was 18.7 wt%, and the aliphatic hydrocarbon concentration T was 25.1 wt%.

Synthesis of polyimide precursor (polymer A-9):

In the synthesis of the above polymer A-1, 95.93 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane and 89.8 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane were used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-9. The weight average molecular weight (Mw) of the polymer A-9 was measured and found to be 21,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-9 was 20.0 wt%, and the aliphatic hydrocarbon concentration T was 6.5 wt%.

Synthesis of polyimide precursor (polymer A-10):

In the synthesis of the above polymer A-1, 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-10. The weight average molecular weight (Mw) of the polymer A-10 was measured and found to be 16,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-10 was 16.7 wt%, and the aliphatic hydrocarbon concentration T was 22.3 wt%.

Synthesis of polyimide precursor (polymer A-11):

93.7 g of 4,4'-(4,4'-isopropyldiphenoxy)diphthalic anhydride as an acid component was added to a 1-liter separable flask, and 175 g of γ-butyrolactone was added. The γ-butyrolactone solution prepared by dissolving 4.7 g of 2-isocyanatoethyl methacrylate and 28.9 g of pyridine in 20 g of γ-butyrolactone was added over 5 minutes while stirring at room temperature. The mixture was heated at 50°C for 1 hour, and then 48.7 g of 2-hydroxyethyl methacrylate (HEMA) was added. The mixture was further heated at 50°C for 4 hours. After the heat generated by the reaction subsided, 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 69.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a solution of 34.0 g of m-TB as a diamine component dissolved in 110 g of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2.5 hours, 15 g of ethanol was added and stirred for 30 minutes, followed by the addition of 150 g of γ-butyrolactone. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 2700 g of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst ^TM 15" manufactured by Organo Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 8000 g of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdered polymer A-11. The weight average molecular weight (Mw) of the polymer A-11 was measured to be 22,000, the amide group concentration U of each repeating unit was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%.

(A) Synthesis of polyimide precursor (polymer A-12):

93.7 g of 4,4'-(4,4'-isopropyldiphenoxy)diphthalic anhydride as the acid component was added to a 1-liter separable flask, 48.7 g of 2-hydroxyethyl methacrylate (HEMA) and 175 g of γ-butyrolactone were added, 28.5 g of pyridine was added while stirring at room temperature, and heated at 50°C for 4 hours. After the heat generated by the reaction subsided, it was cooled to room temperature. Then it was left to stand for 16 hours to obtain a reaction mixture.

Next, 4.7 g of 2-isocyanatoethyl methacrylate and 0.4 g of pyridine were dissolved in 20 g of γ-butyrolactone, and the γ-butyrolactone solution was added over 5 minutes while being stirred, and heated at 50°C for 7 hours. After the heat generated by the reaction subsided, it was cooled to room temperature. Then it was left to stand for 16 hours to obtain a reaction mixture.

Next, under ice cooling, a solution of 69.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added while stirring for 40 minutes. Next, a solution of 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) as a diamine component dissolved in 110 g of γ-butyrolactone was added while stirring for 60 minutes. After stirring at room temperature for 2.5 hours, 15 g of ethanol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 2700 g of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst ^TM 15" manufactured by Organo Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 8000 g of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdered polymer A-12. The weight average molecular weight (Mw) of the polymer A-12 was measured to be 15,000, the amide group concentration U of each repeating unit was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%.

Synthesis of polyimide precursor (polymer A-13):

In the synthesis of the above polymer A-1, 147.1 g of BPDA was used instead of 155.1 g of ODPA, and 85.8 g of diaminodiphenyl ether was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. In addition, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-13. The weight average molecular weight (Mw) of the polymer A-13 was measured and found to be 22,000. The acyl imide group concentration U of each repeating unit of the polyimide obtained from polymer A-13 was 30.5 wt%, and the aliphatic hydrocarbon group concentration T was 0 wt%.

Synthesis of polyimide precursor (polymer A-14):

In the synthesis of the above polymer A-1, 92.88 g of m-TB was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-14. The weight average molecular weight (Mw) of the polymer A-14 was measured and found to be 19,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-14 was 28.8 wt%, and the aliphatic hydrocarbon concentration T was 6.2 wt%.

Synthesis of polyimide precursor (polymer A-15):

In the synthesis of the above polymer A-1, 179.59 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, thereby obtaining polymer A-15. The weight average molecular weight (Mw) of the polymer A-15 was measured and found to be 22,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-15 was 20.5 wt%, and the aliphatic hydrocarbon concentration T was 4.4 wt%.

Synthesis of polyimide precursor (polymer A-16):

In the synthesis of the above polymer A-1, 309.29 g of 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl]-4,4'-diyl=bis(1,3-dioxy-1,3-dihydro-2-benzofuran-5-carboxylate) was used instead of 155.1 g of ODPA, and 179.59 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. The reaction was carried out in the same manner as described in the synthesis of polymer A-1, thereby obtaining polymer A-16. The weight average molecular weight (Mw) of the polymer A-16 was measured and found to be 29,000. The imide group concentration U of each repeating unit of the polyimide obtained from polymer A-16 is 14.1wt%, and the aliphatic hydrocarbon concentration T is 12.1wt%.

[Manufacturing of photosensitive resin composition]

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

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

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

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

C-1: γ-butyrolactone (GBL)

C-2: Dimethyl sulfoxide (DMSO)

D-1: 3-Glyceryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

D-2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

D-3: (3-triethoxysilylpropyl)-tert-butyl carbamate

Silane coupling agent D-4: Ureaylpropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

Free radical polymerizable compound E-1: 1,9-nonanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Free radical polymerizable compound E-2: 1,6-hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Free radical polymerizable compound E-3: Polyoxypropylene bisphenol A diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

Thermal crosslinking agent F-1: BMI-5100 (manufactured by Yamato Chemical Industries, Ltd.)

Thermal cross-linking agent F-2: SBB70P (manufactured by Asahi Kasei)

Filler G-1: K180SP-CY1 (manufactured by Admatechs)

<Implementation Example 1>

As shown in Table 1, a negative photosensitive resin composition was prepared using the following method using polyimide precursor A-1, and the prepared composition was evaluated. A-1: 100 g as (A) polyimide precursor, B-1: 5 g as (B) photopolymerization initiator, and GBL: 180 g as (C) solvent were dissolved in DMSO: 20 g. A small amount of GBL was then added to adjust the viscosity of the obtained solution to about 40 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 2 below.

<Implementation Examples 2~26, Comparative Examples 1~3>

A negative photosensitive resin composition identical to that of Example 1 was prepared except that the formulation ratios were as shown in Tables 1, 3, and 5 below, and the same evaluation as that of Example 1 was performed. The results are shown in Tables 2, 4, and 6 below.

As shown in Tables 1 to 6, the dielectric loss tangent (Df) of the photosensitive resin compositions of Examples 1 to 27 at 40 GHz is lower than that of Comparative Examples 1 to 3, showing a value of 0.0059 to 0.012. In addition, in the photosensitive resin compositions of Examples 1 to 27, the product of the moisture permeability and the dielectric loss tangent is 3.91 to 9.41, which is lower than the value of the comparative example. The developing time of Comparative Examples 1 and 2 is longer, and the resolution of Comparative Example 1 is "D".

[Industrial availability]

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

Claims (18)

A photosensitive resin composition comprises: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5-10 parts by weight of a photosensitive agent; and (C) 100-300 parts by weight of a solvent. In the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350° C., the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit comprising a structure derived from tetracarboxylic dianhydride and diamine, i.e., the imide group concentration U, is 12 wt %-26 wt %. The resin comprises a structure represented by the following general formula (14):

{wherein, R ₁₅ is an organic group having 1 to 5 carbon atoms, R ₁₆ , R ₁₇ and R ₁₈ are each independently a single bond that can form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group having 6 to 10 carbon atoms and containing an aromatic ring, m ₉ is an integer selected from 1 to 4, m ₁₀ , m ₁₁ and m ₁₂ are each independently an integer selected from 0 to 4, Z ₂ is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the above-mentioned resin}. The photosensitive resin composition of claim 1, wherein in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, the ratio of the total molecular weight of aliphatic hydrocarbons to the molecular weight of the repeating units containing the structure derived from tetracarboxylic dianhydride and diamine compound, i.e., the aliphatic hydrocarbon concentration is 4wt%~35wt%. A photosensitive resin composition as claimed in claim 1 or 2, wherein the structure represented by general formula (14) is derived from a diamine. A photosensitive resin composition as claimed in claim 1 or 2, wherein the resin is a polyimide precursor. The photosensitive resin composition of claim 4, wherein the polyimide precursor comprises a structure represented by the following general formula (4):

{wherein, _X1 is a tetravalent organic group having 6 to 40 carbon atoms, _Y1 is a divalent organic group having 6 to 40 carbon atoms, _n1 is an integer of 2 to 150, _R4 and _R5 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R4 and _R5 is a group represented by the following general formula (5)}

{wherein, R ₆ , R ₇ and R ₈ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10}. A photosensitive resin composition comprises: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5-10 parts by weight of a photosensitizer; and (C) 100-300 parts by weight of a solvent. When the resin comprises a polyimide precursor, the polyimide precursor is represented by the following general formula (4):

{wherein, _X1 is a tetravalent organic group having 6 to 40 carbon atoms, _Y1 is a divalent organic group having 6 to 40 carbon atoms, _n1 is an integer of 2 to 150, _R4 and _R5 are independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein at least one of _R4 and _R5 is a group represented by the following general formula (5)}

{wherein, R ₆ , R ₇ and R ₈ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10} The above resin comprises a structure represented by the following general formula (15):

{wherein, Rz each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and may form a ring structure, a represents an integer of 0 to 4, A each independently represents an oxygen atom or a sulfur atom, and B is one of the following formulae:

The above resin comprises a structure represented by the following general formula (14):

{wherein, R ₁₅ is an organic group having 1 to 5 carbon atoms, R ₁₆ , R ₁₇ and R ₁₈ are each independently a single bond that can form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group having 6 to 10 carbon atoms and containing an aromatic ring, m ₉ is an integer selected from 1 to 4, m ₁₀ , m ₁₁ and m ₁₂ are each independently an integer selected from 0 to 4, Z ₂ is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the above-mentioned resin}. A photosensitive resin composition comprising: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5 to 10 parts by weight of a photosensitive agent; and (C) 100 to 300 parts by weight of a solvent; wherein the photosensitive resin composition is heated and cured at 350° C. to obtain a polyimide cured film. In the above, the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic dianhydride and diamine is set as the imide group concentration U, and the ratio of the total molecular weight of the aliphatic hydrocarbon group is set as the aliphatic hydrocarbon group concentration T, U is 12wt%~26wt%, and satisfies the following formula (1): -12.6<U-T<16.0 (1). A photosensitive resin composition comprises: (A) 100 parts by weight of at least one resin selected from polyimide and polyimide precursor; (B) 0.5-10 parts by weight of a photosensitive agent; and (C) 100-300 parts by weight of a solvent; in the IR spectrum of the polyimide obtained by heating and curing the polyimide precursor (A) at 230° C., the maximum peak intensity of the absorption peak in the range of 1450 cm ^-1 or more and 1550 cm ^-1 or less is defined as Ph ₁ , the peak intensity of the second intensity is defined as Ph ₂ , the peak intensity near 1380 cm -1 is defined as Im ₁ , and the peak intensity near 1550 cm ^-1 is defined as Ph 2 . When ₁ is normalized to 1, the following formula (2) is satisfied: 0.34≦Ph ₂ ×Im ₁ ≦1.2 (2). A photosensitive resin composition as claimed in any one of claims 1, 2, 6 to 8, wherein the resin is a reaction product of tetracarboxylic dianhydride and diamine. The photosensitive resin composition of claim 9, wherein at least one of the tetracarboxylic dianhydrides and at least one of the diamines constituting the resin have an aliphatic hydrocarbon group. The photosensitive resin composition of any one of claims 1, 2, 6 to 8 further comprises (D) a silane coupling agent. The photosensitive resin composition of any one of claims 1, 2, 6 to 8 further comprises (E) a free radical polymerizable compound. As in claim 12, the photosensitive resin composition, wherein (E) the free radical polymerizable compound has an alkyl group. The photosensitive resin composition of any one of claims 1, 2, 6 to 8 further comprises (F) a thermal crosslinking agent. The photosensitive resin composition of any one of claims 1, 2, 6 to 8 further comprises (G) filler. A method for producing a polyimide cured film comprises the following steps: applying a photosensitive resin composition as described in any one of claims 1 to 15 on a substrate to form a photosensitive resin layer on the substrate; heating and drying the obtained photosensitive resin layer; exposing the heated and dried photosensitive resin layer; developing the exposed photosensitive resin layer; and heating the developed photosensitive resin layer to form a polyimide cured film. As in claim 16, the method for manufacturing a polyimide cured film, wherein the steps from coating to developing are performed in such a way that a photosensitive resin layer with a film thickness of 10 μm to 15 μm is obtained in the developing step, and the developing time during the developing is less than 30 seconds. A photosensitive resin composition as claimed in any one of claims 1, 2, 6 to 8, wherein the photosensitive resin composition is used for redistribution layer purposes.