CN116710498A

CN116710498A - Polyimide precursor resin composition and method for producing same

Info

Publication number: CN116710498A
Application number: CN202280009745.7A
Authority: CN
Inventors: 村上航平; 小仓知士
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2021-01-12
Filing date: 2022-01-12
Publication date: 2023-09-05

Abstract

The purpose of the present disclosure is to provide a method for producing a PI precursor resin composition that has excellent resolution, a wide usable exposure range, and excellent handleability. Provided is a method for producing a Polyimide (PI) precursor resin composition containing a PI precursor resin, an exposure light absorber, a photopolymerization initiator, and a solvent. The PI precursor resin is selected from materials having an absorbance parameter Xp of the light type in the range of 0.001 to 0.20, the exposure light absorber is selected from materials having an absorbance parameter Xt of the light type in the range of 0.01 to 0.05, and the photopolymerization initiator is selected from materials having an absorbance parameter Xr of the light type in the range of 0 to 0.04. The addition mass part α of the exposure light absorber and the addition mass part β of the photopolymerization initiator are determined so as to satisfy the following formula based on the envisaged thickness D of the film formed by coating the PI precursor resin composition into a film and desolvating. (Xp+Xt x alpha+Xr x beta) x D is more than or equal to 0.7 and less than or equal to 2.2.

Description

Polyimide precursor resin composition and method for producing same

Technical Field

The present disclosure relates to a polyimide precursor resin composition, a method for producing the same, and the like.

Background

Polyimide (PI) resins have excellent heat resistance, electrical characteristics, and chemical resistance, and are therefore used for insulating materials for electronic parts, passivation films for semiconductor devices, surface protective films, interlayer insulating films, and the like. The photosensitive polyimide obtained by imparting photosensitivity to the polyimide resin is provided in the form of a polyimide precursor resin composition (also referred to as "varnish") containing a polyimide precursor resin and a photosensitive agent, and a relief pattern of the polyimide can be formed by applying the varnish, exposing, developing, and thermally imidizing the polyimide by curing. The formation of the relief pattern of a non-photosensitive polyimide requires the application and release of a resist material, and such a photosensitive polyimide precursor resin has a feature that the process can be greatly shortened.

On the other hand, in recent years, from the viewpoints of improvement in integration level and arithmetic functions, and reduction in chip size, a method for mounting a semiconductor device on a printed wiring board (package structure) has also been changed. Specifically, from the conventional mounting method using a metal needle and a lead-tin eutectic solder, a structure has been gradually changed in which a polyimide film such as a BGA (ball grid array) or CSP (chip size package) capable of being mounted at a higher density is used to directly contact with the solder bumps. Further, a structure having a plurality of rewiring layers having an area larger than the area of a semiconductor chip on the surface of the semiconductor chip such as FO (fan-out) has been proposed (for example, refer to patent documents 1 and 2).

With the miniaturization and high density of such packages, high resolution performance is required for the resin film forming the rewiring layer.

Prior art literature

Patent literature

Patent document 1 Japanese patent laid-open publication No. 2005-167191

Patent document 2 Japanese patent application laid-open No. 2011-129767

Disclosure of Invention

Problems to be solved by the invention

When a negative photosensitive resin composition is used as the PI precursor resin composition, if the exposure light does not properly converge at the film bottom during exposure patterning, the exposure light reflected at the film bottom may cause residues to be generated at the development opening and cause development failure. In addition, if the exposure light does not reach the film bottom, photocrosslinking of the film bottom may become insufficient, causing a defective tapered shape called undercut (undercut). Accordingly, an object of the present disclosure is to provide a PI precursor resin composition having excellent resolution, a wide usable exposure range, and excellent handleability. These problems are remarkably generated when PI precursor resin compositions are coated to be thin, when PI precursor resin compositions having low absorbance of exposure light are used.

Solution for solving the problem

The present inventors have found that PI precursor resin compositions comprising PI precursor resin, exposure light absorber, photopolymerization initiator and solvent can be provided with excellent resolution performance, a wide usable exposure range and excellent handleability by determining the composition by a specific method based on the light absorbance parameters for PI precursor resin, exposure light absorber and photopolymerization initiator for the type of light used in exposure. Examples of embodiments of the present disclosure are listed in items [1] to [43] below.

[1] A method for producing a PI precursor resin composition comprising a Polyimide (PI) precursor resin, an exposure light absorber, a photopolymerization initiator, and a solvent, the method comprising:

a step of determining the type of light used for exposure;

selecting the PI precursor resin from the resins having absorbance parameters Xp in the range of 0.001 to 0.20 for the specified light type, selecting the exposure light absorber from the materials having absorbance parameters Xt in the range of 0.01 to 0.05 for the specified light type, and selecting the photopolymerization initiator from the materials having absorbance parameters Xr in the range of 0 to 0.04 for the specified light type;

a step of determining the addition mass part (a) of the exposure light absorber and the addition mass part (β) of the photopolymerization initiator based on the absorbance parameter (Xp) of the PI precursor resin selected, the absorbance parameter (Xt) of the exposure light absorber selected, the absorbance parameter (Xr) of the photopolymerization initiator selected, and the desired thickness (D) of the pre-baked film obtained by coating the PI precursor resin composition with a film and desolvating the film so as to satisfy the following formula,

(Xp+Xt x alpha+Xr x beta) x D is more than or equal to 0.7 and less than or equal to 2.2; and

and a step of preparing a PI precursor resin composition so as to contain the PI precursor resin specified, the exposing light absorber specified in the additive mass part α, the photopolymerization initiator specified in the additive mass part β, and a solvent.

[2] The production method according to item 1, wherein the PI precursor resin has a structural unit represented by the following formula (1),

{ in X ₁ An organic group of valence 4, Y ₁ An organic group of valence 2, n ₁ Is an integer of 2 to 150, and R ₁ R is R ₂ Each independently represents a hydrogen atom, a 1-valent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms. }

{ in which R ₃ 、R ₄ R is R ₅ Each independently is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ Is an integer of 2 to 10. }.

[3] The production method according to item 1 or 2, wherein the type of light used for the exposure is i-rays.

[4] The production method according to any one of items 1 to 3, wherein the addition mass part α of the exposure light absorber and the addition mass part β of the photopolymerization initiator are determined by setting the assumed thickness D to 1 μm or more and less than 7 μm.

[5] The process according to any one of items 1 to 4, wherein the photopolymerization initiator has an oxime ester structure represented by the following general formula (5),

{ in which R ₁₆ 、R ₁₇ R is R ₁₈ Organic groups each having a valence of 1, R ₁₆ R is R ₁₇ Optionally interconnected to form a ring structure. }.

[6] The production method according to any one of items 1 to 5, wherein the PI precursor resin composition further comprises a nitrogen-containing heterocyclic rust inhibitor.

[7] The production method according to any one of items 1 to 6, wherein the exposure light absorber is a compound having a 1, 2-naphthoquinone diazide structure.

[8] The production method according to any one of items 1 to 7, wherein the PI precursor resin composition further comprises a photopolymerizable compound.

[9]The production method according to any one of items 1 to 8, wherein Y of the above formula (1) ₁ Is a 2-valent organic group represented by the following formula (3),

{ in which R ₆ ～R ₁₃ Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R ₆ ～R ₁₃ At least 1 of which is methyl, trifluoromethyl or methoxy. }.

[10]The production method according to any one of items 1 to 9, wherein Y of the above formula (1) ₁ Is a 2-valent organic group represented by the following formula (4),

{ in which R ₁₄ 、R ₁₅ Each independently is methyl, trifluoromethyl or methoxy. }.

[11] The production method according to any one of items 1 to 10, wherein the exposure light absorber is 1, 2-naphthoquinone diazide-4-sulfonate and/or 1, 2-naphthoquinone diazide-5-sulfonate of at least 1 hydroxyl compound selected from the group consisting of the following general formulae (6) to (10),

{ in formula (6), X ₁ X is X ₂ Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 60 carbon atoms, X ₃ X is X ₄ Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 60 carbon atoms, r1, r2, r3, and r4 are each independently an integer of 0 to 5, at least 1 of r3 and r4 is an integer of 1 to 5, r1+r3=5, and r2+r4=5. }

[ chemical 7]

{ in formula (7), Z represents a 4-valent organic group having 1 to 20 carbon atoms, X ₅ 、X ₆ 、X ₇ X is X ₈ Each independently represents a 1-valent organic group having 1 to 30 carbon atoms, r6 is an integer of 0 or 1, r5, r7, r8, and r9 are each independently an integer of 0 to 3, r10, r11, r12, and r13 are each independently an integer of 0 to 2, and at least 1 of r10, r11, r12, and r13 is 1 or 2.}

{ in formula (8), r14 represents an integer of 1 to 5, r15 is an integer of 3 to 8, r14×r15L each independently represents a 1-valent organic group having 1 to 20 carbon atoms, r 15T each independently represents a hydrogen atom or a 1-valent organic group having 1 to 20 carbon atoms, and r 15S each independently represents a hydrogen atom or a 1-valent organic group having 1 to 20 carbon atoms. }

{ in formula (9), a represents a 2-valent organic group containing an aliphatic tertiary carbon or quaternary carbon, and M represents a 2-valent organic group. }

{ in formula (10), r17, r18, r19 and r20 are each independently an integer of 0 to 2, at least 1 of r17, r18, r19 and r20 is 1 or 2, X ₁₀ ～X ₁₉ Each independently represents at least 1 valence 1 group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y ₁ ～Y ₃ Are each independently selected from the group consisting of single bonds, -O-, -S-, -SO ₂ -、-CO-、-CO ₂ -at least 1 valence 2 group of the group consisting of cyclopentylene, cyclohexylene, phenylene and valence 2 organic groups having 1 to 20. }.

[12] The production method according to any one of items 1 to 11, wherein the exposure light absorber is 1, 2-naphthoquinone diazide-5-sulfonate of at least one hydroxyl compound selected from the group consisting of the formulas (6) to (10).

[13] The production method according to any one of items 1 to 12, wherein the esterification rate of the exposure light absorber is 80% or more.

[14] The production method according to any one of items 1 to 13, wherein the hydroxyl compound represented by the general formula (6) is represented by the following general formula (11),

{ in formula (11), r20 is each independently an integer of 0 to 2, and X ₉ Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. }.

[15] A method of making a relief pattern film, said method comprising:

a step of producing a PI precursor resin composition containing a PI precursor resin, an exposure light absorber, a photopolymerization initiator, and a solvent by the method according to any one of items 1 to 14;

a coating step of obtaining a coating film of the PI precursor resin composition;

a drying step of desolventizing the solvent in the coating film to obtain a photosensitive resin layer having a thickness D';

an exposure step of exposing the photosensitive resin layer to light according to the determined light type; and

and a developing step of developing the photosensitive resin layer after the exposure to obtain a relief pattern film.

[16] The method for producing a relief pattern film according to item 15, wherein the coating film having a thickness D' after desolvation is:

0.7≤(Xp+Xt×α+Xr×β)×D’≤2.2。

[17] a PI precursor resin composition comprising a PI precursor resin, an exposure light absorber in an amount of alpha based on 100 parts by mass of the PI precursor resin, a photopolymerization initiator in an amount of beta, and a solvent,

Absorbance parameter Xp of the PI precursor resin for i-ray,

Absorbance parameter Xt of the exposure light absorber for i-rays,

Absorbance parameter Xr of the photopolymerization initiator for i-ray,

The mass part alpha of the exposure light absorber and

the relation of the mass parts beta of the photopolymerization initiator is as follows:

0.7≤(Xp+Xt×α+Xr×β)×10≤2.2

0.001≤Xp≤0.20

0.01≤Xt≤0.05

0≤Xr≤0.04。

[18] a PI precursor resin composition comprising a Polyimide (PI) precursor resin, an alpha-ray absorber in parts by mass based on 100 parts by mass of the PI precursor resin, a beta-ray photopolymerization initiator and a solvent,

absorbance parameter Xp of the PI precursor resin for i-ray,

Absorbance parameter Xt of the exposure light absorber for i-rays,

Absorbance parameter Xr of the photopolymerization initiator for i-ray,

The mass part alpha of the exposure light absorber and

0.7≤(Xp+Xt×α+Xr×β)×5≤2.2

0.001≤Xp≤0.20

0.01≤Xt≤0.05

0≤Xr≤0.04。

[19] the PI precursor resin composition according to item 17 or 18, wherein the PI precursor resin has a structural unit represented by the following formula (1),

[20] The PI precursor resin composition according to any one of items 17-19, wherein the photopolymerization initiator has an oxime ester structure represented by the following general formula (5),

[ chemical 14]

[21] The PI precursor resin composition according to any one of items 17 to 20, wherein the PI precursor resin composition further comprises a nitrogen-containing heterocyclic rust inhibitor.

[22] The PI precursor resin composition according to any one of items 17 to 21, wherein the exposure light absorber is a compound having a 1, 2-naphthoquinone diazide structure.

[23] The PI precursor resin composition according to any one of items 17 to 22, wherein the PI precursor resin composition further comprises a photopolymerizable compound.

[24]The PI precursor resin composition according to any one of items 17-23, wherein Y of the formula (1) ₁ Is a 2-valent organic group represented by the following formula (3),

[25]The PI precursor resin composition according to any one of items 17-24, wherein Y of the formula (1) ₁ Is a 2-valent organic group represented by the following formula (4),

[26] The PI precursor resin composition according to any one of items 17-25, wherein the exposure light absorber is 1, 2-naphthoquinone diazide-4-sulfonate and/or 1, 2-naphthoquinone diazide-5-sulfonate of at least 1 hydroxy compound selected from the group consisting of the following general formulae (6) to (10),

{ in formula (7), Z represents a 4-valent organic group having 1 to 20 carbon atoms，X ₅ 、X ₆ 、X ₇ X is X ₈ Each independently represents a 1-valent organic group having 1 to 30 carbon atoms, r6 is an integer of 0 or 1, r5, r7, r8, and r9 are each independently an integer of 0 to 3, r10, r11, r12, and r13 are each independently an integer of 0 to 2, and at least 1 of r10, r11, r12, and r13 is 1 or 2.}

[27] The PI precursor resin composition according to any one of items 17 to 26, wherein the exposure light absorber is 1, 2-naphthoquinone diazide-5-sulfonate of at least one hydroxy compound selected from the group consisting of formulas (6) to (10).

[28] The PI precursor resin composition according to any one of items 17 to 27, wherein the esterification rate of the exposure light absorber is 80% or more.

[29] The PI precursor resin composition according to any one of items 17 to 28, wherein the hydroxyl compound represented by the general formula (6) is represented by the following general formula (11),

{ in formula (11), r16 is each independently an integer of 0 to 2, and X ₉ Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. }.

[30] The cured film of the PI precursor resin composition according to any one of items 17 to 29.

[31] A pre-baked film having a thickness D 'of 1 μm.ltoreq.D'. Ltoreq.20 μm and comprising a Polyimide (PI) precursor resin composition,

the PI precursor resin composition contains a PI precursor resin, an exposure light absorber in an amount of alpha parts by mass relative to 100 parts by mass of the PI precursor resin, and a photopolymerization initiator in an amount of beta parts by mass relative to 100 parts by mass of the PI precursor resin,

the absorbance parameter Xp of the PI precursor resin for i-rays is in the range of 0.001-0.20,

the absorbance parameter Xt of the exposure light absorber for i rays is in the range of 0.01-0.05,

the absorbance parameter Xr of the photopolymerization initiator for i-rays is in the range of 0-0.04,

The pre-baked film satisfies the following formula:

0.7≤(Xp+Xt×α+Xr×β)×D’≤2.2。

[32] the pre-baked film according to item 31, wherein the PI precursor resin has a structural unit represented by the following formula (1),

[33] The pre-baked film according to item 31 or 32, wherein the thickness D 'of the pre-baked film is 1 μm.ltoreq.D' < 7. Mu.m.

[34] The pre-baked film according to any of items 31 to 33, wherein the photopolymerization initiator has an oxime ester structure represented by the following general formula (5),

[35] The pre-baked film according to any of items 31 to 34, wherein the PI precursor resin composition further comprises a nitrogen-containing heterocyclic rust inhibitor.

[36] The pre-baked film according to any one of items 31 to 35, wherein the exposing light absorber is a compound having a 1, 2-naphthoquinone diazide structure.

[37] The pre-baked film according to any of items 31 to 36, wherein the PI precursor resin composition further comprises a photopolymerizable compound.

[38]The pre-baked film according to any of items 31 to 37, wherein Y of the above formula (1) ₁ Is a 2-valent organic group represented by the following formula (3),

[39]The pre-baked film according to any of items 31 to 38, wherein Y of the above formula (1) ₁ Is a 2-valent organic group represented by the following formula (4),

[40] The pre-baked film according to any one of items 31 to 39, wherein the exposure light absorber is 1, 2-naphthoquinone diazide-4-sulfonate and/or 1, 2-naphthoquinone diazide-5-sulfonate of at least 1 hydroxyl compound selected from the group consisting of the following general formulae (6) to (10),

[41] The pre-baked film according to any one of items 31 to 40, wherein the exposure light absorber is 1, 2-naphthoquinone diazide-5-sulfonate of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

[42] The pre-baked film according to any of items 31 to 41, wherein the esterification rate of the exposing light absorber is 80% or more.

[43] The pre-baked film according to any of items 31 to 42, wherein the hydroxyl compound represented by the general formula (6) is represented by the following general formula (11),

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, a method for producing a PI precursor resin composition having excellent resolution, a wide usable exposure range, and excellent handleability can be provided.

Drawings

FIG. 1 is a photograph of the FIB of the cross-sectional shape of the pattern obtained in example 1.

Fig. 2 is a sensitivity curve obtained by plotting the relative film thickness at each exposure amount of the relief pattern obtained in example 50.

Detailed Description

Method for producing PI precursor resin composition

The method for producing a PI precursor resin composition of the present disclosure is a method for producing a PI precursor resin composition comprising (a) a Polyimide (PI) precursor resin, (B) an exposure light absorber, (C) a photopolymerization initiator, and (D) a solvent, the method comprising: a step of determining the type of light used for exposure; a material selection step of selecting a polyimide precursor resin, an exposure light absorber, and a photopolymerization initiator; a content determination step of determining an addition mass part alpha of the exposure light absorber and an addition mass part beta of the photopolymerization initiator; and a step of preparing a PI precursor resin composition.

Light type determining process

In the light type determining step, the type of light used for exposing the PI precursor resin composition is determined. As the light type, any light type may be used as long as the polymerizable group of the polyimide precursor resin can be crosslinked by the action of the photopolymerization initiator at the time of exposing the PI precursor resin composition to light so as to be insoluble with respect to the developer. Examples of the type of light include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm wavelength), and KrF excimer laser (248 nm wavelength), and i-rays are preferable from the viewpoints of insolubilization of polyimide precursor resin, resolution, and the like.

Material selection procedure

In the material selection step, (A) a polyimide precursor resin, (B) an exposure light absorber, and (C) a photopolymerization initiator are selected based on absorbance parameters for the selected light type. (D) The solvent is not dependent on the type of light selected and may be arbitrarily selected. In addition to these, other materials may be further selected, such as (E) a photopolymerizable compound, a thermolyzing agent, (H) a nitrogen-containing heterocyclic rust inhibitor, (F) a hindered phenol compound, an organic titanium compound, an adhesion promoter, a sensitizer, or (G) a polymerization inhibitor, or the like, or a combination of these, irrespective of the kind of light selected. Other materials including (E), (F) and (G) are also not dependent on the type of light selected and may be arbitrarily selected.

(A) Selection of polyimide precursor resins

The polyimide precursor resin is a resin component contained in the negative photosensitive resin composition, and is converted into polyimide by performing a heat cyclization treatment. The polyimide precursor resin is selected from resins having absorbance parameters Xp in the range of 0.001 to 0.20 for the determined light type. Regarding the absorbance of the polyimide precursor resin, the polyimide precursor resin may be prepared to 1000mg/L using N-methyl-2-pyrrolidone as a solvent, and measured using an ultraviolet-visible spectrophotometer using a cuvette of 1 cm. The absorbance value at 365nm was divided by 10, and the obtained value was defined as the absorbance parameter Xp of the polyimide precursor resin. The polyimide precursor resin is selected from resins having an absorbance parameter Xp in the range of preferably 0.001 to 0.15, more preferably 0.005 to 0.10, and still more preferably 0.005 to 0.05. The polyimide precursor resin is not limited in structure as long as it can be used in the negative photosensitive resin composition, and is preferably not alkali-soluble. By making the polyimide precursor resin not alkali-soluble, higher chemical resistance can be obtained. When the negative photosensitive resin composition contains 2 or more polyimide precursor resins, the absorbance parameter Xp of the mixture of the 2 or more polyimide precursor resins for the specified light type may be in the range of 0.001 to 0.20. The absorbance parameters Xp of the 2 or more polyimide precursor resins for the specified light types are preferably selected so as to be all in the range of 0.001 to 0.20.

The polyimide precursor resin is preferably a polyamide having a structure represented by the following general formula (1).

{ in formula (1), X ₁ Is a tetravalent organic group, Y ₁ Is a divalent organic group, n ₁ Is an integer of 2 to 150, and R ₁ R is R ₂ Each independently a hydrogen atom, or a monovalent organic group. }

In the general formula (1), R ₁ R is R ₂ At least one of them preferably has a structural unit represented by the following general formula (2),

{ in (2)，R ₃ 、R ₄ R is R ₅ Are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ Is an integer of 2 to 10. }.

R in the general formula (1) ₁ R is R ₂ In the proportion of hydrogen atoms, R ₁ R is R ₂ The total mole number of (2) is more preferably 20% or less, still more preferably 15% or less, still more preferably 5% or less. In addition, R in the general formula (1) ₁ R is R ₂ The ratio of the monovalent organic groups represented by the above general formula (2) is represented by R ₁ R is R ₂ The total mole number of (2) is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. The ratio of the hydrogen atoms and the ratio of the organic groups of the general formula (2) are in the above ranges, and are preferable from the viewpoints of photosensitivity and storage stability.

N in the general formula (1) ₁ The integer is not limited as long as it is 2 to 150, but is preferably 3 to 100, more preferably 5 to 70, from the viewpoints of the photosensitive properties and mechanical properties of the negative photosensitive resin composition.

In the general formula (1), X ₁ The tetravalent organic group is preferably an organic group having 6 to 40 carbon atoms, more preferably-COOR, from the viewpoint of heat resistance and photosensitivity ₁ Radical and-COOR ₂ An aromatic group or an alicyclic aliphatic group in which the group and the-CONH-group are ortho to each other. As X ₁ The tetravalent organic group is specifically an organic group having 6 to 40 carbon atoms and containing an aromatic ring, for example, a group having a structure selected from the group consisting of the following general formula (I),

in the formula { wherein R6 is selected from the group consisting of a hydrogen atom, a fluorine atom, and C ₁ ～C ₁₀ Monovalent hydrocarbon radicals and C ₁ ～C ₁₀ At least 1 of the group consisting of monovalent fluorine-containing hydrocarbon groups, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4Is an integer of (a). But are not limited to these. In addition, X ₁ The number of the structures may be 1 or a combination of 2 or more. X having the structure represented by the above formula (I) ₁ The base is particularly preferable from the viewpoint of both heat resistance and photosensitivity.

As X ₁ In the structure represented by the above formula (I), the radical preferably contains a tetravalent organic group represented by the following formula,

wherein R6 is at least 1 selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3. }. By providing the polyimide precursor resin with such a structure, heat resistance and resolution can be improved.

In the general formula (1), Y ₁ The divalent organic group is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of heat resistance and photosensitivity, and examples thereof include a structure represented by the following formula (II),

in the formula { wherein R6 is selected from the group consisting of a hydrogen atom, a fluorine atom, and C ₁ ～C ₁₀ Monovalent hydrocarbon radicals and C ₁ ～C ₁₀ At least 1 of the group consisting of monovalent fluorine-containing hydrocarbon groups, and n is an integer selected from 0 to 4. But are not limited to these. In addition, Y ₁ The number of the structures may be 1 or a combination of 2 or more. Y having the structure represented by the above formula (II) ₁ The base is particularly preferable from the viewpoint of both heat resistance and photosensitivity.

As Y ₁ Among the structures represented by the above formula (II), a divalent group represented by the following formula is particularly preferable from the viewpoints of heat resistance, chemical resistance and resolution,

in the formula, R6 is at least 1 selected from the group consisting of fluorine atoms, monovalent hydrocarbon groups having 1 to 10 carbon atoms and monovalent fluorine-containing hydrocarbon groups having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4. }.

As Y ₁ In the structure represented by the above formula (II), a divalent group represented by the following formula (3) is more preferable,

{ in which R ₆ ～R ₁₃ Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R ₆ ～R ₁₃ At least 1 of which is methyl, trifluoromethyl or methoxy. }. By providing the polyimide precursor resin with such a rigid structure, swelling of the film during development can be suppressed, and extremely high resolution can be exhibited.

As Y ₁ In the structure represented by the above formula (II), a divalent group represented by the following formula (4) is further preferable,

{ in which R ₁₄ 、R ₁₅ Each independently is methyl, trifluoromethyl or methoxy. }. By providing the polyimide precursor resin with such a rigid structure, swelling of the film during development can be suppressed, and extremely high resolution can be exhibited.

(A) Preparation method of polyimide precursor resin

Regarding the polyimide precursor resin, first, a polyimide precursor resin containing the aforementioned tetravalent organic group X ₁ The tetracarboxylic dianhydride of (a) is reacted with an alcohol having a photopolymerizable unsaturated double bond and optionally an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester). After which the mixture is madePartially esterified tetracarboxylic acids with a radical comprising the abovementioned divalent organic radicals Y ₁ The diamine of (2) is subjected to amide polycondensation, thereby obtaining the catalyst.

(preparation of acid/ester body)

Organic group X containing tetravalent groups as suitable for preparing polyimide precursor resins ₁ As the tetracarboxylic dianhydride having the structure represented by the above general formula (I), for example, pyromellitic dianhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, diphenyl sulfone-3, 3', 4' -tetracarboxylic dianhydride, diphenylmethane-3, 3',4,4' -tetracarboxylic dianhydride, 2-bis (3, 4-phthalic anhydride) propane, 2-bis (3, 4-phthalic anhydride) -1, 3-hexafluoropropane, and the like, preferably, pyromellitic anhydride, diphenyl ether-3, 3',4,4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, but are not limited thereto. These may be used alone or in combination of 2 or more.

Examples of the alcohols having a photopolymerizable unsaturated double bond suitable for the preparation of the polyimide precursor resin include 2-acryloyloxy ethanol, 1-acryloyloxy-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, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxy ethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-cyclohexyloxy propyl methacrylate.

Examples of the above-mentioned alcohols having a photopolymerizable unsaturated double bond include alcohols having no unsaturated double bond such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

As the polyimide precursor resin, a non-photosensitive polyimide precursor resin prepared using only the above alcohol having no unsaturated double bond may be mixed with the photosensitive polyimide precursor resin to be used. From the viewpoint of resolution, the non-photosensitive polyimide precursor resin is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

The desired acid/ester can be obtained by stirring, dissolving and mixing the tetracarboxylic dianhydride and the alcohol in a solvent such as pyridine in the presence of an alkaline catalyst, as described later, to thereby carry out the esterification reaction of the acid anhydride. The stirring and dissolution and mixing are preferably carried out at a temperature of 20 to 50℃for 4 to 24 hours, for example.

(preparation of polyimide precursor resin)

The acid/ester compound (typically, in the form of a solution in a solvent described below) can be converted into a polyanhydride by adding an appropriate dehydration condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, N' -disuccinimide carbonate, or the like to the acid/ester compound under ice-cooling and mixing. Dropping a divalent organic group Y into a polyacid anhydride of an acid/ester ₁ The diamine is separately dissolved or dispersed in a solvent, and subjected to amide polycondensation, whereby a polyimide precursor resin can be obtained. Alternatively, the acid/ester may be obtained by subjecting the acid moiety to acid chlorination with thionyl chloride or the like, and then reacting the acid moiety with a diamine compound in the presence of a base such as pyridine or the like.

As another synthesis method, a polyimide precursor resin can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound in advance to obtain a polyamic acid, and then introducing the above-mentioned alcohol into the carboxylic acid portion of the side chain of the obtained polyamic acid using an appropriate dehydration condensing agent such as trifluoroacetic anhydride.

As a compound comprising a divalent organic radical Y ₁ The diamine having a structure represented by the general formula (II) above, examples thereof include p-phenylenediamine, m-phenylenediamine, 4-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfide, and 4,4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 4 '-diaminobiphenyl, 3' -diaminobiphenyl, 4 '-diaminobenzophenone, 3' -diaminobenzophenone 4,4 '-diaminodiphenylmethane, 3' -diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [ 4- (4-aminophenoxy) phenyl ] sulfone, bis [ 4- (3-aminophenoxy) phenyl ] sulfone, 4-bis (4-aminophenoxy) biphenyl, 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-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis [ 4- (4-aminophenoxy) phenyl ] hexafluoropropane, 1, 4-bis (3-aminopropyldimethylsilyl) benzene, o-tolylsulfone, and 9, 9-bis (4-aminophenyl) fluorene; and those wherein a part of hydrogen atoms on the benzene ring are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen or the like, such as 3,3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminodiphenylmethane, 2 '-dimethyl-4, 4' -diaminodiphenylmethane, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dichloro-4, 4' -diaminobiphenyl; and Mixtures thereof, and the like, but is not limited thereto.

After the completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydration condensing agent present in the reaction liquid is filtered off as needed. Then, a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Further, the polymer is purified by repeating the redissolution and reprecipitation operation, etc., and vacuum drying is performed to separate the polyimide precursor resin of interest. In order to improve the degree of purification, the ionic impurities may be removed by passing the solution of the polymer through a column in which an anion and/or cation exchange resin is swollen and packed with an appropriate organic solvent.

The molecular weight of the polyimide precursor resin is preferably 8,000 ～ 150,000, more preferably 9,000 to 50,000, when measured as a weight average molecular weight in terms of polystyrene by gel permeation chromatography. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when the weight average molecular weight is 150,000 or less, the dispersibility in a developer is good, and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are preferable. The weight average molecular weight was obtained from a standard curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is preferably selected from organic solvent standard samples STANDARD SM-105 manufactured by Showa electric company.

(B) Selection of exposure light absorber

The exposure light absorber is selected from materials having an absorbance parameter Xt in the range of 0.01 to 0.05 for the determined light type. Within the above range, the absorbance of the film can be precisely adjusted by the appropriate addition amount range. When the absorbance parameter Xt is less than 0.01, a large amount of the light absorbing agent is required to be added when adjusting the absorbance, which may cause precipitation of the exposure light absorbing agent or inhibit other side effects such as performance. On the other hand, when the absorbance parameter Xt is larger than 0.05, a small amount of addition also causes rapid change in absorbance of the film, and thus precise adjustment is difficult. Regarding the absorbance of the exposure light absorber, the exposure light absorber can be prepared to 10mg/L using N-methyl-2-pyrrolidone as a solvent, and measured using an ultraviolet-visible spectrophotometer using a cuvette of 1 cm. The value of absorbance at 365nm obtained was divided by 10, and the value obtained was defined as absorbance parameter Xt of the exposure light absorber. The exposure light absorber is selected from materials having an absorbance parameter Xt in a range of preferably 0.015 to 0.040, more preferably 0.015 to 0.03, and still more preferably 0.015 to 0.025. When the negative photosensitive resin composition contains 2 or more exposure light absorbers, the absorbance parameter Xt of the mixture of the 2 or more exposure light absorbers for the specified light type may be in the range of 0.01 to 0.05. The absorbance parameters Xt of the 2 or more exposure light absorbers for the specified light types are preferably all selected to be in the range of 0.01 to 0.05.

The exposure light absorber is preferably at least one compound selected from the group consisting of preferably a 2- (2' -hydroxyphenyl) benzotriazole-based compound, a hydroxyphenyl triazine-based compound, a 2-hydroxybenzophenone-based compound, a cyanoacrylate-based compound, an azobenzene-based compound, a polyphenol-based compound, and a compound having a quinone azide group. Specific examples of the exposure light absorber include 2- (hydroxyphenyl) compounds such as 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol ], 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 6- (2-benzotriazolyl) -4-tert-butyl-4 ' -methyl-2, 2' -methylenebisphenol, 2- (2 ' -hydroxy-3 ',5' -di-tert-pentylphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -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-amyl-2-hydroxyphenyl) benzotriazole;

hydroxyphenyl triazine compounds such as 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-tert-octyloxyphenyl) -1,3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2,4, 6-tris (4-butoxy-2-hydroxyphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, bis-ethylhexyloxyphenol methoxyphenyl triazine (bemotriazinol), 2,4, 6-tris (2, 4-dihydroxyphenyl) -1,3, 5-triazine;

2-hydroxybenzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone, 2', 4' -tetrahydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate;

cyanoacrylate compounds, azobenzene compounds, catechin, rutin, cyanidin, curcumin and other polyphenol compounds, quinone azide compounds (hereinafter also referred to as "quinone diazide compounds"), and the like.

Among them, the quinone diazide compound is preferable as the exposing light absorber from the viewpoint of resolution performance. Examples of the quinone diazide compound include a compound having a 1, 2-benzoquinone diazide structure and a compound having a 1, 2-naphthoquinone diazide structure, and they are known from the specification of U.S. Pat. No. 2,772,972, the specification of U.S. Pat. No. 2,797,213, the specification of U.S. Pat. No. 3,669,658, and the like. The quinone diazide compound is more preferably at least one compound selected from the group consisting of a 1, 2-naphthoquinone diazide-4-sulfonate of a polyhydroxy compound having a specific structure and a 1, 2-naphthoquinone diazide-5-sulfonate of the polyhydroxy compound (hereinafter also referred to as "NQD compound") which will be described in detail below, from the viewpoints of resolution performance and the sectional shape of the pattern to be formed. The reason for this is not limited in theory, but it is considered that the NQD compound that absorbs the exposure light undergoes an intramolecular rearrangement reaction, and the light absorption ability disappears, so that the light reaching amount at the bottom of the film can be appropriately adjusted. In addition, the NQD compound is excellent in solubility in a solvent as compared with other exposure light absorbers. Thus, even when a polyimide precursor resin having low absorbance of exposure light is used and the film thickness to be used is small, the absorbance of the coating film can be adjusted by adding a large amount of the NQD compound.

The NQD compound can be obtained by forming a sulfonyl chloride from a naphthoquinone diazide sulfonic acid compound with chlorosulfonic acid or thionyl chloride and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a condensation reaction with a polyhydroxy compound according to a conventional method. For example, the obtained product can be obtained by reacting a predetermined amount of a polyhydroxy compound with 1, 2-naphthoquinone diazide-5-sulfonyl chloride or 1, 2-naphthoquinone diazide-4-sulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran in the presence of an alkaline catalyst such as triethylamine to esterify the resulting product, washing with water, and drying the resulting product.

The compound having a quinone diazide group is preferably a 1, 2-naphthoquinone diazide-4-sulfonate and/or a 1, 2-naphthoquinone diazide-5-sulfonate compound of at least 1 hydroxyl compound selected from the group consisting of the following general formulae (6) to (10).

{ in formula (6), X ₁ X is X ₂ Each independently represents a hydrogen atom or a C1-60, preferably C1-30, 1-valent organic group, X ₃ X is X ₄ Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 60 carbon atoms, preferably 1 to 30 carbon atoms, r1, r2, r3 and r4 are each independently integers of 0 to 5, at least 1 of r3 and r4 is an integer of 1 to 5, r1+r3=5, and r2+r4=5. }

{ in formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14×r15L each independently represents a 1-valent organic group having 1 to 20 carbon atoms, r 15T each independently represents a hydrogen atom or a 1-valent organic group having 1 to 20 carbon atoms, and r 15S each independently represents a hydrogen atom or a 1-valent organic group having 1 to 20 carbon atoms. }

In the formula (9), a preferably represents at least 1 of 2-valent groups selected from 3 groups represented by the following chemical formulas.

{ in formula (10), r17, r18, r19 and r20 are each independently an integer of 0 to 2, at least 1 of r17, r18, r19 and r20 is 1 or 2, X ₁₀ ～X ₁₉ Each independently represents at least 1 valence 1 group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y ₁ ～Y ₃ Are each independently selected from the group consisting of single bonds, -O-, -S-, -SO ₂ -、-CO-、-CO ₂ -at least 1 valence 2 group of the group consisting of cyclopentylene, cyclohexylene, phenylene and valence 2 organic groups having 1 to 20. }

In the above general formula (10), Y ₁ ～Y ₃ Preferably at least 1 of 3 organic groups having a valence of 2, each independently selected from the group consisting of the following general formula,

{ in X ₂₀ X is X ₂₁ Are each independently selected from the group consisting of hydrogen atoms, alkyl groups, and alkene groupsAt least 1 of the groups 1, X ₂₂ 、X ₂₃ 、X ₂₄ X is X ₂₅ Each independently represents a hydrogen atom or an alkyl group, r21 is an integer of 1 to 5, and X ₂₆ 、X ₂₇ 、X ₂₈ X is X ₂₉ Each independently represents a hydrogen atom or an alkyl group. }.

The compound represented by the general formula (6) is preferably a hydroxyl compound represented by the following formulas (11) and (17) to (20), and more preferably a hydroxyl compound represented by the formula (11).

{ in formula (11), r20 is each independently an integer of 0 to 2, and X ₉ Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. X is X ₉ When there are plural, plural X' s ₉ Optionally the same or different, respectively.

In the formula (11), X ₉ Preferably a 1-valent organic group represented by the following chemical formula,

in the formula { formula, r18 is an integer of 0 to 2, X ₃₁ Represents at least 1 organic group having 1 valence selected from the group consisting of hydrogen atom, alkyl group and cycloalkyl group, and when r18 is 2, 2X ₃₁ Optionally the same or different from each other. }.

{ in formula (17), X ₃₂ Represents at least 1 organic group having 1 valence selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and a cycloalkyl group having 1 to 20 carbon atoms. }

{ in formula (18), r19 is an integer of 0 to 2, X ₃₃ Each independently represents a hydrogen atom or a 1-valent organic group represented by the following general formula, and X ₃₄ Represents at least 1 selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.

(wherein r20 is an integer of 0 to 2, X ₃₅ Represents at least 1 selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group, and when r20 is 2, 2X' s ₃₅ Optionally the same or different from each other. ) }

The compound represented by the above formula (20) is p-cumylphenol.

The hydroxyl compounds represented by the following formulas (21) to (23) are preferable as the compound represented by the above formula (11) because they have high sensitivity when forming NQD compounds and have low precipitation in PI precursor resin compositions (NQD compounds of polyhydroxy compounds described in japanese patent application laid-open publication No. 2004-109849).

The hydroxyl compound represented by the following formula (24) is preferable as the compound represented by the above formula (17) because of its high sensitivity when forming NQD compounds and its low precipitation in PI precursor resin compositions (NQD compounds of polyhydroxy compounds described in japanese patent application laid-open No. 2001-356475).

The hydroxyl compounds represented by the following formulas (25) to (27) are preferable as the compound represented by the above (18) because of high sensitivity when forming NQD compounds and low precipitation in PI precursor resin compositions (NQD compounds of polyhydroxy compounds described in japanese patent application laid-open No. 2005-8626).

In the above general formula (7), Z is not particularly limited as long as Z is a 4-valent organic group having 1 to 20 carbon atoms, and is preferably a 4-valent group having a structure represented by the following formula from the viewpoint of sensitivity.

Among the compounds represented by the above general formula (7), hydroxyl compounds represented by the following formulas (28) to (31) are preferable because of high sensitivity in forming NQD compounds and low precipitation in PI precursor resin compositions (NQD compounds of polyhydroxy compounds described in japanese patent application laid-open No. 2001-92138).

The hydroxyl compound represented by the above general formula (8) is preferably a polyhydroxy compound NQD compound described in japanese patent application laid-open No. 2004-347902 because of its high sensitivity when forming NQD compound and low precipitation in PI precursor resin composition.

In the formula {, r40 is an integer of 0 to 9 independently. }

The hydroxyl compounds represented by the following formulas (33) and (34) are preferable as the compounds represented by the general formula (9) because of high sensitivity and low precipitation in PI precursor resin compositions when forming NQDs.

Specific examples of the compound represented by the above general formula (10) include NQDs of a polyhydroxy compound described in japanese patent application laid-open No. 2001-109149. Among these compounds, NQD compounds of the polyhydroxy compound represented by the following formula (35) are preferable because of high sensitivity and low precipitation in PI precursor resin compositions.

In the quinone diazide compound, the 1, 2-naphthoquinone diazide sulfonyl group has excellent resolution when it is either 1, 2-naphthoquinone diazide-5-sulfonyl group or 1, 2-naphthoquinone diazide-4-sulfonyl group, and the 1, 2-naphthoquinone diazide-5-sulfonyl group has more excellent resolution.

In the quinone diazide compound, the average esterification rate of the naphthoquinone diazide sulfonyl ester of the hydroxyl compound is preferably 60% or more and 100% or less, more preferably 80% or more and 100% or less from the viewpoint of resolution. The reason for this is presumed to be that swelling upon development is suppressed by esterifying the hydroxyl group in the (B') quinone diazide compound.

In the present embodiment, one or both of the 1, 2-naphthoquinone diazide-4-sulfonate compound and the 1, 2-naphthoquinone diazide-5-sulfonate compound are preferably selected. Alternatively, a 1, 2-naphthoquinone diazide sulfonate compound having a 1, 2-naphthoquinone diazide-4-sulfonyl group and a 1, 2-naphthoquinone diazide-5-sulfonyl group in the same molecule may be used, or a 1, 2-naphthoquinone diazide-4-sulfonate compound and a 1, 2-naphthoquinone diazide-5-sulfonate compound may be used in combination.

(C) Photopolymerization initiator

The photopolymerization initiator is selected from materials having absorbance parameters Xr in the range of 0 to 0.04 for the determined light type. Regarding the absorbance of the photopolymerization initiator, the photopolymerization initiator can be prepared to 10mg/L using N-methyl-2-pyrrolidone as a solvent, and measured using an ultraviolet-visible spectrophotometer using a cuvette of 1 cm. The value of absorbance at 365nm obtained was divided by 10, and the value obtained was defined as the absorbance parameter Xr of the photopolymerization initiator. The photopolymerization initiator is selected from compounds having an absorbance parameter Xr in the range of preferably 0 to 0.03, more preferably 0 to 0.02, and still more preferably 0 to 0.01. When the negative photosensitive resin composition contains 2 or more photopolymerization initiators, the absorbance parameter Xr of the mixture of the 2 or more photopolymerization initiators for the specified light type may be in the range of 0 to 0.04. The 2 or more photopolymerization initiators are preferably selected so that the absorbance parameters Xr of the specified light types are all in the range of 0 to 0.04.

The photopolymerization initiator is preferably a photo radical polymerization initiator, and benzophenone derivatives such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4' -methyldiphenyl ketone, dibenzyl ketone, fluorenone and the like are preferably exemplified; acetophenone derivatives such as 2,2' -diethoxyacetophenone, 2-hydroxy-2-methylpropaneketone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone and diethyl thioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal and benzil-beta-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; oximes such as 1-phenyl-1, 2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (o-benzoyl) oxime, 1, 3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, and 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime; n-arylglycine such as N-phenylglycine; photoacid generators such as peroxides (e.g., benzoyl peroxide), aromatic biimidazoles, titanocenes, and α - (n-octanesulfonyloxy imino) -4-methoxybenzyl cyanide; photobase generators such as 9-anthracenemethyl-N, N-diethylcarbamate, etc., but are not limited thereto. Among the photopolymerization initiators, oximes are more preferable, especially from the standpoint of photosensitivity.

Among the oxime photopolymerization initiators, a compound having an oxime ester structure represented by the following general formula (5) is preferable from the standpoint of photosensitivity.

{ in which R ₁₆ 、R ₁₇ R is R ₁₈ Organic groups each having a valence of 1, R ₁₆ And R is R ₁₇ Optionally interconnected to form a ring structure. }

Among the compounds having the oxime ester structure of the above formula (5), at least one compound selected from the group consisting of the following formulas (5A), (5B) and (5C) is more preferable from the standpoint of photosensitivity.

{ in formula (5A), R ₁ Is methyl or phenyl, R ₂ Is a hydrogen atom or a 1-valent organic group having 1 to 12 carbon atoms, R ₃ Is alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms or phenyl. }

{ in formula (5B), Z is a sulfur or oxygen atom, and R ₄ Represents methyl, phenyl, R ₅ ～R ₇ Each independently represents a hydrogen atom or a 1-valent organic group. }

{ in formula (5C), R ₈ An aromatic group having 6 to 20 carbon atoms, a 1-valent organic group derived from a heterocyclic compound having 5 to 20 carbon atoms, R ₉ Is alkyl with 1-5 carbon atoms, R ₁₀ Is an alkyl group having 1 to 10 carbon atoms or a 1-valent organic group having a saturated alicyclic structure having 3 to 10 carbon atoms, R ₁₁ Represents methyl or ethyl, propyl, phenyl. }

(D) Solvent(s)

Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, alcohols, and the like, and for example, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol (phenyl glycol), tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, methylene chloride, 3-methoxy-N, N-dimethylpropionamide, 1, 2-dichloroethane, 1, 4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like can be used. Among them, from the viewpoints of solubility of the resin, stability of the resin composition, and adhesion to a substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N, N-dimethylpropionamide, benzyl alcohol, phenyl ethylene glycol, and tetrahydrofurfuryl alcohol are preferable.

Among these solvents, a solvent which can completely dissolve the polymer produced is particularly preferable, and examples thereof include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, 3-methoxy-N, N-dimethylpropionamide, tetramethylurea, and γ -butyrolactone. The number of solvents may be 1, or 2 or more solvents may be used in combination.

The amount of the solvent used in the PI precursor resin composition is preferably in the range of 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, based on 100 parts by mass of the polyimide precursor resin.

The PI precursor resin composition may further contain components other than the above-described components (a) to (D) (hereinafter also referred to as "other components"). The other components than the components (a) to (D) are not limited, and examples thereof include (E) a photopolymerizable compound, a thermolyzing agent, (H) a nitrogen-containing heterocyclic rust inhibitor, (F) a hindered phenol compound, an organic titanium compound, an adhesion promoter, a sensitizer, and (G) a polymerization inhibitor. Of the materials contained in the "other component", the materials having absorbance parameters Xt of 0.01 to 0.05 are in principle "exposure light absorber". Among the materials contained in the "other component", a compound that has an absorbance parameter Xt of 0.01 to 0.05 and itself absorbs light and supplies the obtained energy to other compounds to promote the improvement of the sensitivity of the system belongs to the "sensitizer". By using a sensitizer, the system becomes highly sensitive, and as a result, the usable exposure range is narrowed, and the formation of residues at the bottom of the unexposed portion tends to be promoted, and the effect opposite to that of the exposure light absorber is exhibited. Among the materials contained in the "other component", the nitrogen-containing heterocyclic compound having an absorbance parameter Xt of 0.01 to 0.05 and having an interaction site with the copper interface such as an imino group or an amino group belongs to the group (H) "nitrogen-containing heterocyclic rust inhibitor". Among the materials contained in the "other component", a compound having an absorbance parameter Xt of 0.01 to 0.05 and having an interaction site with the silicon wafer interface such as an alkoxysilane structure belongs to the "adhesion promoter". This is because these "nitrogen-containing heterocyclic rust inhibitors" and "adhesion promoters" are present in the vicinity of the wafer interface in a biased manner, and therefore do not have the effect of adjusting the absorbance of the entire film. Therefore, those belonging to the group consisting of "sensitizer", "nitrogen-containing heterocyclic rust inhibitor" and "adhesion promoter" are not regarded as "exposure light absorber" even if the value of absorbance parameter Xt is 0.01 to 0.05.

(E) Photopolymerizable compound

The PI precursor resin composition preferably further comprises a photopolymerizable compound. The photopolymerizable compound is a monomer having a photopolymerizable unsaturated bond, which can be formed by assisting crosslinking of the polyimide precursor resin by exposure to light. As such a monomer, (meth) acrylic compounds in which radical polymerization is performed by a photopolymerization initiator are preferable. Examples of the photopolymerizable compound include, but are not limited to, ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, and mono-or diacrylates and methacrylates of polyethylene glycol; mono-or diacrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, di-or triacrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylate; diacrylates and dimethacrylates of 1, 4-butanediol; diacrylates and dimethacrylates of 1, 6-hexanediol; diacrylate and dimethacrylate of neopentyl glycol; mono-or di-acrylates and methacrylates of bisphenol A; benzene trimethyl acrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and methacrylate; di-or triacrylates and methacrylates of glycerol; di-, tri-, or tetra-acrylates and methacrylates of pentaerythritol; and ethylene oxide or propylene oxide adducts of these compounds.

When the PI precursor resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass relative to 100 parts by mass of the polyimide precursor resin. When the amount of the compound is 1 part by mass or more, good sensitivity can be obtained at the time of exposure, and when 50 parts by mass or less, the in-plane uniformity of the coating film is excellent.

Thermal alkaline producing agent

The PI precursor resin composition may contain an alkaline generator. The alkaline generator is a compound that generates a base by heating. By containing the thermal alkaline generator, imidization of the PI precursor resin composition can be further promoted.

The type of the thermal alkaline agent is not particularly limited, and examples thereof include amine compounds protected by t-butoxycarbonyl groups and thermal alkaline agents disclosed in International publication No. 2017/038598. However, the present invention is not limited to these, and other known thermoalcogens may be used.

As the amine compound protected by the t-butoxycarbonyl group, examples thereof include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1, 3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexane ethanol, 4- (2-aminoethyl) cyclohexanol, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, alpha- [2- (methylamino) ethyl ] benzyl alcohol, diethanolamine, diisopropylamine, 3-pyrrolidinol, 2-pyrrolidinol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, piperidine, 4-hydroxypiperidine, 2-ethanol, piperidine, 2-ethanol and the like, 2- (4-piperidinyl) -2-propanol, 1, 4-butanol bis (3-aminopropyl) ether, 1, 2-bis (2-aminoethoxy) ethane, 2' -oxydiethylamine, 1, 14-diamino-3, 6,9, 12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis (3-aminopropyl) ether, 1, 11-diamino-3, 6, 9-trioxaundecane, or compounds in which the amino group of amino acids and derivatives thereof is protected with t-butoxycarbonyl groups, but are not limited thereto.

The blending amount of the thermal alkaline generator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the polyimide precursor resin (a). The blending amount is 0.1 part by mass or more from the viewpoint of the imidization promoting effect, and preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing the PI precursor resin composition.

(H) Nitrogen-containing heterocyclic rust inhibitor

In forming a cured film on a substrate containing copper or a copper alloy using the PI precursor resin composition, the PI precursor resin composition optionally contains a nitrogen-containing heterocyclic rust inhibitor in order to suppress discoloration on copper. Examples of the nitrogen-containing heterocyclic rust inhibitor include an azole compound and a purine derivative. Among them, the 2- (2' -hydroxyphenyl) benzotriazole compound does not have a coordination site with copper and is not contained in the nitrogen-containing heterocyclic rust inhibitor. The nitrogen-containing heterocyclic rust inhibitor is preferably a compound having an imino group or an amino group.

Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4, 5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, 1, 5-dimethyltriazole, 4, 5-diethyl-1H-triazole, 1H-benzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

Among them, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole and 5-amino-1H-tetrazole are preferable. In addition, 1 kind of these azole compounds may be used, or a mixture of 2 or more kinds may be used.

Specific examples of the purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2, 6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-dimethyladenine, 2-fluoroadenine, guanine oxime, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylamino purine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) guanine, N- (3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

The compounding amount of the PI precursor resin composition when the azole compound or the purine derivative is contained is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, from the viewpoint of the photosensitivity property, relative to 100 parts by mass of the (a) polyimide precursor resin. When the compounding amount of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor resin (a), discoloration of the copper or copper alloy surface is suppressed when the PI precursor resin composition is formed on copper or copper alloy, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent.

(F) Hindered phenol compound

In order to suppress discoloration on the copper surface, the PI precursor resin composition optionally contains a hindered phenol compound. Examples of the hindered phenol compound include, but are not limited to, 2, 6-di-t-butyl-4-methylphenol, 2, 5-di-t-butyl-hydroquinone, octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 4 '-methylenebis (2, 6-di-t-butylphenol), 4' -thio-bis (3-methyl-6-t-butylphenol), 4 '-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2-thio-diethylenebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylenebis (3, 5-di-t-butyl-4-hydroxyphenyl) 2, 6-hydroxybutyl-2-methylpropenyl) propionate, and 2-t-butylidene-2-4-hydroxy-2-methyl-4-p-hydroxy-5-butylphenol Pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the like.

In addition, as the hindered phenol compound, examples thereof include 1,3, 5-tris (3-hydroxy-2, 6-dimethyl-4-isopropylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-sec-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione 1,3, 5-tris [4- (1-ethylpropyl) -3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris [ 4-triethylmethyl-3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (3-hydroxy-2, 6-dimethyl-4-phenylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 5, 6-trimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5, 6-diethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-2, 5-hydroxy-methylbenzyl) -1,3, 5-trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-trione, 1,3, 5-tris (4-tert-butyl-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3, 5-dimethylbenzyl) -trione, but is not limited thereto. Of these, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and the like are particularly preferred.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, from the viewpoint of the light sensitivity characteristics, relative to 100 parts by mass of the (a) polyimide precursor resin. When the compounding amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor resin (a), for example, discoloration and corrosion of copper or copper alloy can be prevented when the PI precursor resin composition is formed on copper or copper alloy, while when it is 20 parts by mass or less, the photosensitivity is excellent.

Organic titanium compound

The PI precursor resin composition may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

Examples of the usable organic titanium compound include compounds in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII):

i) Titanium chelate compound: among them, titanium chelates having 2 or more alkoxy groups are more preferable from the viewpoint of storage stability of the PI precursor resin composition and obtaining a good pattern. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (n-butoxy) bis (2, 4-pentanedione) diisopropoxide bis (2, 4-pentanedione) titanium, titanium diisopropoxide bis (tetramethylheptanedione) titanium, titanium diisopropoxide bis (ethylacetoacetate), and the like.

II) titanium tetraalkoxide compounds: for example, titanium tetra-n-butoxide, titanium tetra-ethoxide, titanium tetra (2-ethylhexoxide), titanium tetra-isobutanooxide, titanium tetra-isopropoxide, titanium tetra-methoxide, titanium tetra-methoxypropanoate, titanium tetra-methylphenoxide, titanium tetra-n-nonanol, titanium tetra-n-propoxide, titanium tetra-stearyl alcohol, titanium tetra [ bis {2,2- (allyloxymethyl) butanol } ], and the like.

III) titanocene compound: for example, pentamethylcyclopentadienyl trimethoxytitanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.

IV) titanium monoalkoxide compound: such as titanium isopropoxide tris (dioctyl phosphate), titanium isopropoxide tris (dodecylbenzenesulfonate), and the like.

V) titanium oxide compound: such as bis (glutaryl) titanium oxide, bis (tetramethylheptanedioyl) titanium oxide, oxytitanium phthalocyanine, and the like.

VI) titanium tetra acetylacetonate compound: for example, titanium tetra-acetylacetonate, and the like.

VII) titanate coupling agent: such as isopropyl tri (dodecylbenzenesulfonyl) titanate, and the like.

Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) titanium tetraalkoxide compound, and III) titanocene compound from the viewpoint of exhibiting more excellent chemical resistance. Particularly preferred are diisopropoxybis (ethylacetoacetate) titanium, tetra-n-butoxide titanium and bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.

The blending amount of the organic titanium compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the (a) polyimide precursor resin. When the amount of the compound is 0.05 parts by mass or more, the heat resistance and chemical resistance are excellent, and when it is 10 parts by mass or less, the storage stability is excellent.

Bonding aid

In order to improve the adhesion of a film formed using the PI precursor resin composition to a substrate, the PI precursor resin composition optionally contains an adhesion promoter. Examples of the adhesion promoter include adhesion promoters such as gamma-aminopropyl dimethoxy silane, N- (. Beta. -aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, gamma-glycidoxypropyl methyl dimethoxy silane, gamma-mercaptopropyl methyl dimethoxy silane, 3-methacryloxypropyl dimethoxy methyl silane, 3-methacryloxypropyl trimethoxy silane, dimethoxymethyl-3-piperidyl propyl silane, diethoxy-3-glycidoxypropyl methyl silane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl ] phthalamic acid, benzophenone-3, 3 '-bis (N- [ 3-triethoxysilyl ] propyl amide) -4,4' -dicarboxylic acid, benzene-1, 4-bis (N- [ 3-triethoxysilyl ] propyl amide) -2, 5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, N-phenylaminopropyl trimethoxy silane, 3-ureidopropyl triethoxy silane, 3- (trialkoxysilyl) propyl anhydride, aluminum (acetyl) silane coupling agent such as aluminum (acetyl) aluminum (ethyl acetate), aluminum (acetyl) and the like.

Among these adhesion promoters, a silane coupling agent is more preferably used from the viewpoint of adhesion. When the PI precursor resin composition contains an adhesion promoter, the compounding amount of the adhesion promoter is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the (a) polyimide precursor resin.

The silane coupling agent is not limited, and examples thereof include 3-mercaptopropyl trimethoxysilane (manufactured by Xinyue chemical Co., ltd.: trade name KBM803, manufactured by chisso Co., ltd.) trade name Silaace S810), 3-mercaptopropyl triethoxysilane (manufactured by Azmax corporation: trade name of SIM 6475.0), 3-mercaptopropyl methyl dimethoxy silane (trade name of LS1375, trade name of Azmax manufactured by Xin Yue chemical Co., ltd., product name of SIM 6474.0), mercaptomethyl trimethoxy silane (trade name of Azmax Co., ltd., product name of SIM6473.5C), mercaptomethyl dimethoxy silane (trade name of Azmax Co., ltd., product name of SIM 6473.0), 3-mercaptopropyl diethoxy methoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, 3-mercaptopropyl diethoxy propoxy silane, 3-mercaptopropyl ethoxy dipropoxy silane, 3-mercaptopropyl dimethoxy silane, 2-mercaptoethyl trimethoxy silane, 2-mercaptoethyl diethoxy methoxy silane, 2-mercaptoethyl triethoxy silane, 2-mercaptoethyl diethoxy dimethoxy silane, 2-mercaptoethyl dimethoxy propoxy silane, 2-mercaptoethyl propoxy silane, 4-mercaptobutyl dimethoxy silane, 4-mercapto ethoxy propoxy silane, and butyl trimethoxy silane, 4-mercaptobutyl tripropoxy silane, and the like.

Further, as the silane coupling agent, there are no limitations, and examples thereof include N- (3-triethoxysilylpropyl) urea (trade name LS3610, trade name SIU9055.0, trade name Azmax, trade name SIU9058.0, N- (3-diethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropylpropyl) urea, N- (3-ethoxydipropylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxypropylsilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-tripropylsilylethyl) urea, N- (3-triethoxysilylethyl) urea, N- (3-ethoxydiethoxypropylethyl) urea, N- (3-dimethoxysilylethyl) urea, N- (3-trimethoxysilylethyl) urea, and N- (3-trimethoxysilylethyl) urea N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Co., ltd.: trade name SLA 0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., ltd.: trade name SLA 0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., ltd.: trade name SLA 0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Co., ltd.: trade name SLA 0599.2) and the like.

Further, as the silane coupling agent, for example, 2- (trimethoxysilylethyl) pyridine (Azmax Co., ltd.: trade name: SIT 8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-t-butoxysilane, tetra (methoxyethoxysilane), tetra (methoxy-n-propoxysilane), tetra (ethoxyethoxysilane), tetra (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl ] disulfide, bis [3- (triethoxysilyl) propyl ] diethoxysilane, di-t-butoxysilane, di-butoxyphenylsilane, di-tert-butoxysilane, tri-ethoxysilane, methylphenyl silanol, ethylphenyl silanol, n-propylphenyl silanol, isopropylphenyl silanol, n-butyldiphenyl silanol, isobutylphenyl silanol, t-butylphenyl silanol, diphenylsilanol, dimethoxydiphenyl silanol, diethoxydiphenyl silane, dimethoxydi-p-tolyl silanol, ethylmethylphenyl silanol, n-propylmethylphenyl silanol, isopropylmethylphenyl silanol, n-butylmethylphenyl silanol, isobutylphenyl silanol, t-butylmethylphenyl silanol, ethyl-n-propylphenyl silanol, ethylisopropylphenyl silanol, n-butylethylphenyl silanol, isobutylphenyl silanol, t-butylethylphenyl silanol, methyldiphenyl silanol, ethyldiphenyl silanol, n-propyldiphenyl silanol, isopropyldiphenyl silanol, n-butyldiphenyl silanol, isobutyldiphenyl silanol, t-butyldiphenyl silanol, triphenylsilanol, etc., but is not limited thereto.

The silane coupling agents listed above may be used alone or in combination of two or more. Among the above-listed silane coupling agents, phenylsilanol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent having a structure represented by the following formula are preferable from the viewpoint of storage stability.

The amount of the silane coupling agent to be compounded is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the polyimide precursor resin (a).

Sensitizer

The PI precursor resin composition may optionally contain a sensitizer in order to improve photosensitivity. As a result of the use of the sensitizer, examples thereof include Michler's ketone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 3' -carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N ' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 kinds.

The compounding amount of the PI precursor resin composition when the PI precursor resin composition contains a sensitizer for improving photosensitivity is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (a) polyimide precursor resin.

(G) Polymerization inhibitor

In order to improve the stability of the viscosity and photosensitivity of the PI precursor resin composition, especially when stored in a solution state containing a solvent, the PI precursor resin composition optionally contains a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, N-nitrosodiphenylamine, p-t-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-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, and the like can be used.

Content determining process

In the content determination step, the addition mass part α of the exposure light absorber and the addition mass part β of the photopolymerization initiator are determined from the absorbance parameter Xp of the polyimide precursor resin, the absorbance parameter Xt of the exposure light absorber, the absorbance parameter Xr of the photopolymerization initiator, and the assumed thickness D of the pre-baked film obtained by coating the PI precursor resin composition into a film and desolvating the film according to the following formula (1).

0.7≤(Xp+Xt×α+Xr×β)×D≤2.2 (1)

The parts by mass α and β are parts by mass when the polyimide precursor resin is 100 parts by mass. The inventors have found that the degree of absorption of the type of light (i-rays, for example) varies depending on the skeleton of the PI precursor resin, and therefore it is necessary to adjust the light absorption characteristics of the entire resin composition to the above-described specific range with other components depending on the absorption parameters of the PI precursor resin. Thus, a PI precursor resin composition having excellent resolution performance and a wide range of exposure to be used, which is suitable for the film thickness to be used, can be obtained. The reason for this is not limited in theory, and is considered to be: by setting the absorbance of the PI precursor resin composition-coated film within the range of the above formula (1), the light arrival amount at the bottom of the film at the time of exposure is adjusted, and it is possible to suppress diffuse reflection of the film bottom base substrate and suppress unwanted crosslinking reaction of the unexposed portion.

The value of (xp+xt×α+xr×β) ×d is preferably in the range of 0.7 to 2.2, more preferably in the range of 0.7 to 1.4. (1) When the value of the formula (i) is less than 0.7, a large amount of residue is generated in the development opening by diffuse reflection of the film base substrate at the time of exposure, and good resolution performance cannot be obtained. In addition, when the PI precursor resin composition is prepared so as to satisfy the formula (1) using only a photopolymerization initiator without using an exposure light absorber, the sensitivity to exposure light becomes high, and the usable exposure range becomes narrow, and the handleability becomes low. On the other hand, when the value of the formula (1) exceeds 2.2, the photocuring of the film bottom becomes insufficient, and a tapered shape called undercut (undercut) becomes a problem. (1) When the value of the formula is in the range of 0.7 to 1.4, a pattern having a preferable tapered shape with good resolution can be obtained. The ideal tapered shape in the present disclosure means a shape in which the wall surface angle of the pattern is about 70 ° to 80 °. When the wall angle is 70 ° or more, the coverage of the wiring of the lower layer of the PI cured film is good, and the risk of exposure of the wiring of the lower layer can be reduced, and when the wall angle is 80 ° or less, the deposition of the seed layer sputtering of the RDL wiring formed on the upper layer of the PI cured film is good, and the risk of occurrence of defective formation of the RDL wiring can be reduced.

The predicted thickness D of the pre-baked film is a predicted thickness of the pre-baked film obtained by coating the PI precursor resin composition into a film and desolvating the film. In the present specification, the actual thickness of the pre-baked film of the film obtained by coating the PI precursor resin composition with the film and desolvating is referred to as D' for distinction. The thickness D of the pre-baked film can be set to be preferably 1 μm to 20. Mu.m, more preferably 1 μm to 10. Mu.m, still more preferably 1 μm to less than 7. Mu.m.

Regarding the compounding amount α of the exposure light absorber determined by the above formula (1), when the exposure light is i-rays and the thickness D of the predetermined pre-baked film is 10 μm, for example, 0.1 parts by mass or more and 20 parts by mass or less, 1 part by mass or more and 10 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polyimide precursor resin.

Regarding the compounding amount β of the photopolymerization initiator determined by the above formula (1), when the exposure light is i-ray and the thickness D of the predetermined pre-baked film is 10 μm, for example, it may be 0.1 parts by mass or more and 10 parts by mass, 1 part by mass or more and 8 parts by mass or less, or 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polyimide precursor resin.

PI precursor resin composition preparation Process

In the PI precursor resin composition preparation step, the PI precursor resin composition is prepared so as to contain the specified PI precursor resin, the specified additive mass part α of the exposure light absorber, the specified additive mass part β of the photopolymerization initiator, the solvent, and any other materials selected. More specifically, for example, the PI precursor resin composition can be obtained by adding and mixing the materials to the selected solvent. The viscosity of the PI precursor resin composition can be adjusted to, for example, 10 to 100 poise (poise). The PI precursor resin composition may be filtered, as desired.

Method for producing relief pattern film

The method for manufacturing the relief pattern film comprises the following steps: (1) A step of producing a PI precursor resin composition containing a PI precursor resin, an exposure light absorber, a photopolymerization initiator, and a solvent by the above-described PI precursor resin composition production method; (2) A coating step of obtaining a coating film of the PI precursor resin composition; (3) A drying step of desolventizing the solvent in the coating film to obtain a pre-baked film having a thickness D'; (4) An exposure step of exposing the pre-baked film by the determined light type; and (5) a developing step of developing the photosensitive resin layer after exposure to obtain a relief pattern film.

(1) Process for producing PI precursor resin composition

The present step is a step of producing a PI precursor resin composition by the above-described step of producing a PI precursor resin composition of the present disclosure.

(2) Coating process

In this step, the PI precursor resin composition is coated on an arbitrary substrate to obtain a coating film of the PI precursor resin composition. As the coating method, a method conventionally used for coating PI precursor resin compositions, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like can be used; a method of spray coating by a spray coater, and the like.

(3) Drying process

In this step, the solvent in the coating film of the PI precursor resin composition is desolventized to obtain a pre-baked film of practical thickness D'. The actual thickness D' is the same as or similar to the assumed thickness D, and may be, for example, within a range of about ±5% of the assumed thickness D. The thickness D' is preferably 1 μm to 20. Mu.m, more preferably 1 μm to 10. Mu.m, still more preferably 1 μm to less than 7. Mu.m. Examples of the method of desolvation include a method such as air-drying, heat-drying using an oven or a hot plate, and reduced-pressure or vacuum-drying. Specifically, in the air-drying or heat-drying, the drying may be performed under the condition of 20 to 150 ℃ for 1 minute to 1 hour. The pre-baked film of the thickness D ' after the desolvation more preferably satisfies 0.7.ltoreq.Xp+Xt X. Alpha. + Xr X. Beta.). Times.D '. Ltoreq.2.2, still more preferably 0.7.ltoreq.Xp+Xt X. Alpha. + Xr X. Beta.). Times.D '. Ltoreq.1.4.

(4) Exposure process

In this step, the photosensitive resin layer formed as described above is exposed to light using the specified light type. In exposure, exposure is performed using an exposure apparatus such as a contact aligner, a mirror projector, or a stepper through a photomask or a reticle (reticle) having a pattern, or directly using an ultraviolet light source or the like. By this exposure, the polyimide precursor contained in the PI precursor resin composition of the exposed portion is crosslinked by the photopolymerization initiator, and becomes insoluble in the developer.

(5) Development process

In this step, the photosensitive resin layer is developed after exposure to obtain a relief pattern film. The unexposed portion of the photosensitive resin layer after exposure is removed by contact with a developer. The development method may be any one selected from conventionally known development methods of photoresists, for example, a spin spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. After development, post-development baking may be performed according to need based on any combination of temperature and time for the purpose of adjusting the shape of the relief pattern.

As the developing solution used in the development, for example, a good solvent for the PI precursor resin composition or a combination of the good solvent and a poor solvent is preferable. The good solvent is preferably, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, cyclopentanone, cyclohexanone, gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, or the like. The poor solvent is preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, or the like. When the poor solvent and the poor solvent are mixed and used, the ratio of the poor solvent to the poor solvent is preferably adjusted according to the solubility of the polymer in the PI precursor resin composition. In addition, 2 or more solvents, for example, a plurality of solvents may be used in combination.

Method for producing cured film (cured relief pattern)

The method for producing a cured film of the present disclosure includes a step of curing the relief pattern film produced by the development step (5) to form a cured film (cured relief pattern).

(6) Curing relief pattern formation process

In this step, the relief pattern obtained by the development is subjected to a heat treatment to disperse the photosensitive component and imidize the polyimide precursor resin, thereby converting the relief pattern into a cured relief pattern formed of polyimide. As a method of the heat treatment, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-raising oven capable of performing temperature programming can be selected. The heat treatment may be performed, for example, at 160℃to 350℃for 30 minutes to 5 hours. The temperature of the heat treatment is preferably 250 ℃ or lower, more preferably 200 ℃ or lower. As an atmosphere gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.

Polyimide (polyimide)

According to the present disclosure, a cured film of the PI precursor resin composition is also provided based on the above-described method of manufacturing a cured film. The cured film is the cured relief pattern of polyimide. The imidization ratio of the polyimide is preferably 80 to 100%. The structure of the polyimide contained in the cured film (cured relief pattern) formed from the polyimide precursor resin composition is preferably represented by the following general formula.

{ in the above formula, X ₁ Y and Y ₁ And X in the general formula (1) ₁ Y and Y ₁ Identical, and m is a positive integer. }

X1 and Y1 which are preferable in the general formula (1) are also preferable in the polyimide having the structure shown in the above general formula for the same reason. In the above general formula, the number m of repeating units is not particularly limited, and may be an integer of 2 to 150.

Semiconductor device

According to the present disclosure, there is also provided a semiconductor device having a cured relief pattern obtained by the above-described method of manufacturing a cured relief pattern. For example, a semiconductor device having a substrate as a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described cured relief pattern manufacturing method may be provided. In addition, a method for manufacturing a semiconductor device using a semiconductor element as a base material and including the above-described method for manufacturing a cured relief pattern of the present disclosure as part of a process is also provided. The semiconductor device can be manufactured by forming a cured relief pattern formed by the manufacturing method of the cured relief pattern of the present disclosure as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for semiconductor devices having a bump structure, or the like, in combination with a known manufacturing method of semiconductor devices.

Display device

The present disclosure may provide a display device including a display element and a cured film provided on an upper portion of the display element, the cured film being the cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element or may be laminated with other layers interposed therebetween. Examples of the cured film include surface protective films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA liquid crystal display devices, and partition walls for cathodes of organic EL elements.

The PI precursor resin composition of the present disclosure is preferably a PI precursor resin composition for forming an insulating member or for forming an interlayer insulating film. The PI precursor resin composition is used for the applications such as interlayer insulating films of multilayer circuits, coverlay coatings of flexible copper-clad plates, solder resists, and liquid crystal alignment films, in addition to the above-described applications for semiconductor devices.

Examples

The following will specifically explain examples and comparative examples, but the present disclosure is not limited to these examples.

Production example of polyimide precursor resin (A)

Manufacturing example 1

155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was charged into a 3L-capacity separable flask, 135.4g of 2-hydroxyethyl methacrylate (HEMA) and 400mL of gamma-butyrolactone were added, and the mixture was stirred at room temperature, and 79.1g of pyridine was added while stirring, to obtain a reaction mixture. After the exothermic reaction was completed, the reaction mixture was cooled to room temperature and left for 16 hours. Then, a solution in which 203.3g of Dicyclohexylcarbodiimide (DCC) was dissolved in 180mL of γ -butyrolactone was added to the reaction mixture with stirring for 40 minutes under ice cooling, and then a suspension in which 94.4g of 2,2 '-dimethylbiphenyl-4, 4' -diamine (mTB) was suspended in 300mL of γ -butyrolactone was added with stirring for 60 minutes. After the reaction mixture was further stirred at room temperature for 4 hours, 50mL of ethanol was added, and stirred for 1 hour, and then 500mL of gamma-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 3L of ethanol to form a precipitate formed of a crude polymer. The crude polymer thus obtained was filtered off and dissolved in 1.5L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28L of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum-dried to obtain PI precursor resin A-1 as a polyamic acid ester in the form of powder. As a result of measuring the molecular weight of the PI precursor resin A-1 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 30,000.

The weight average molecular weight (Mw) of the PI precursor resin A-1 was measured by gel permeation chromatography (converted to standard polystyrene) under the following conditions. The column used in the measurement was "Shodex 805M/806M series" manufactured by Showa Denko Co., ltd., the standard monodisperse polystyrene was selected, N-methyl-2-pyrrolidone (NMP) was used as the developing solvent, and "Shodex RI-930" manufactured by Showa Denko Co., ltd., used as the detector.

Manufacturing example 2

155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was charged into a 3L-capacity separable flask, 135.4g of 2-hydroxyethyl methacrylate (HEMA) and 400mL of gamma-butyrolactone were added, and the mixture was stirred at room temperature while 158.2g of pyridine was added thereto, to obtain a reaction mixture. After the exothermic reaction was completed, the reaction mixture was cooled to room temperature and left for 16 hours. 130.9g of thionyl chloride was then added dropwise to the ODPA-HEMA solution with stirring under ice-cooling for 60 minutes to give an acid chloride solution of ODPA. Then, a solution in which 142.3g of 2,2' -bis (trifluoromethyl) benzidine was dissolved in 300mL of NMP was added thereto with stirring for 60 minutes under ice-cooling. After the reaction mixture was further stirred at room temperature for 2 hours, 50mL of ethanol was added and stirred for 1 hour, and then 500mL of gamma-butyrolactone was added.

The obtained reaction solution was added to 3L of ethanol to form a precipitate formed of a crude polymer. The resulting crude polymer was filtered off and dissolved in 1.5L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28L of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum-dried to obtain PI precursor resin A-2 as a polyamic acid ester in the form of powder. The molecular weight of the PI precursor resin a-2 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 28,000.

Manufacturing example 3

The reaction was carried out in the same manner as in production example 1 except that 94.4g of 2,2' -dimethylbiphenyl-4, 4' -diamine (mTB) was used in place of 93.0g of 4,4' -diaminodiphenyl ether (DADPE) in production example 1, to obtain PI precursor resin A-3. The molecular weight of PI precursor resin A-3 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 20,000.

Manufacturing example 4

The reaction was carried out in the same manner as in production example 3 except that 147.1g of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) was used in place of 155.1g of 4,4 '-Oxydiphthalic Dianhydride (ODPA) in production example 3, and the amount of 4,4' -diaminodiphenyl ether (DADPE) was changed to 90.1g, to obtain PI precursor resin A-4. The molecular weight of PI precursor resin A-4 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 30,000.

Manufacturing example 5

The reaction was carried out in the same manner as in production example 3 except that 155.1g of 4,4' -Oxybisphthalic Dianhydride (ODPA) was used in place of 155.1g of 4,4' -Oxybisphthalic Dianhydride (ODPA), and 93.1g of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) was used instead of 87.6g of 4,4' -diaminodiphenyl ether (DADPE) to obtain PI precursor resin a-5. The molecular weight of PI precursor resin A-5 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 20,000.

Manufacturing example 6

The reaction was carried out in the same manner as in production example 1 except that in place of 155.1g of 4,4 '-Oxybisphthalic Dianhydride (ODPA), 112.78g of pyromellitic anhydride (PMDA) and 112.78g of 3,3',4 '-benzophenone tetracarboxylic dianhydride were used and in place of 94.4g of 2,2' -dimethylbiphenyl-4, 4 '-diamine (mTB), 85.10g of 4,4' -diaminodiphenyl ether (DADPE) was used, to obtain PI precursor resin a-6. The molecular weight of PI precursor resin A-6 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 28,000.

Manufacturing example 7

The reaction was carried out in the same manner as in production example 2 except that 91.0g of 2,2' -dimethylbiphenyl-4, 4' -diamine (mTB) was used instead of 142.3g of 2,2' -bis (trifluoromethyl) benzidine in production example 2, to obtain PI precursor resin A-7. The molecular weight of PI precursor resin A-7 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 32,000.

Manufacturing example 8

4,4' -Oxybisphthalic Dianhydride (ODPA) 47.1g, 2-hydroxyethyl methacrylate (HEMA) 5.54g and a catalytic amount of 1, 4-diazabicyclo [2, 2] octane triethylenediamine were dissolved in 380g of NMP, stirred at 45℃for 1 hour and then cooled to 25 ℃. Then 27.4g of 2,2 '-dimethylbiphenyl-4, 4' -diamine (mTB) and 145mL of NMP were added, and the mixture was stirred at 45℃for 150 minutes and then cooled to room temperature. To this solution, 59.7g of trifluoroacetic anhydride was added dropwise, and after stirring for 120 minutes, a catalytic amount of benzoquinone and HEMA40.4g were added, followed by stirring at 45℃for 20 hours. The reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure, whereby PI precursor resin a-8 was obtained. The molecular weight of PI precursor resin A-8 was measured by the same method as in production example 1, and as a result, the weight average molecular weight (Mw) was 35,000.

Synthesis example of (B) an exposure light absorbent

Synthesis example 1

Synthesis of Compound B-1 having 1, 2-naphthoquinone diazide Structure

To a 1L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30.0g (0.707 mol) of 4,4' - (1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylene) bisphenol (trade name: tris-PA, manufactured by Benzhou chemical industry Co., ltd.) represented by the following formula (21) was charged as a hydroxy compound.

53.56g (0.198 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride in an amount corresponding to 93.3 mol% of the OH group of the hydroxyl compound was dissolved in 300g of acetone with stirring, and then added to a flask, and the flask was adjusted to 30℃with a constant temperature bath. Then, 20.0g of triethylamine was dissolved in 18g of acetone, and after being added to a dropping funnel, it was added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, stirring was continued for another 30 minutes, and then hydrochloric acid was added dropwise, followed by stirring for another 30 minutes, to complete the reaction. Thereafter, the reaction was filtered to remove triethylamine hydrochloride. In a 3L beaker, 1640g of pure water and 30g of hydrochloric acid were mixed and stirred, and the filtrate was added dropwise to the mixture while stirring, to obtain a precipitate. The precipitate was washed with water, filtered, and dried under reduced pressure at 40℃for 48 hours to give photosensitive disazo naphthoquinone (B-1).

Synthesis example 2

Synthesis of Compound B-2 having 1, 2-naphthoquinone diazide Structure

A photosensitive diazo naphthoquinone (B-2) was obtained by performing the reaction and purification in the same manner as in Synthesis example 1 except that 47.82g (0.177 mol) of 1, 2-naphthoquinone diazide-4-sulfonyl chloride was used instead of 53.56g (0.198 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride in Synthesis example 1.

Synthetic example 3

Synthesis of Compound B-3 having 1, 2-naphthoquinone diazide Structure

The reaction and purification were carried out in the same manner as described in Synthesis example 1 except that the amount of 1, 2-naphthoquinone diazide-5-sulfonyl chloride (53.56 g, 0.198 mol) in Synthesis example 1 was reduced to 38.26g (0.141 mol), to obtain photosensitive diazo naphthoquinone (B-3).

Synthetic example 4

Synthesis of Compound B-4 having 1, 2-naphthoquinone diazide Structure

To a 1L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30g (0.141 mol) of p-cumylphenol (MITSUI FINE CHEMICALS, INCCo., manufactured by Ltd.) represented by the following formula (20) was charged as a hydroxy compound.

38.1g (0.141 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride in an amount equivalent to 100 mol% of the OH group of the hydroxyl compound was dissolved in 300g of acetone with stirring, and then added to a flask, and the flask was adjusted to 30℃with a constant temperature bath. Then, 17.9g of triethylamine was dissolved in 18g of acetone and added to a dropping funnel, followed by dropping the solution into the flask over 30 minutes. After the completion of the dropwise addition, stirring was continued for another 30 minutes, and then hydrochloric acid was added dropwise, followed by stirring for another 30 minutes, to complete the reaction. Thereafter, the reaction was filtered to remove triethylamine hydrochloride. In a 3L beaker, 1640g of pure water and 30g of hydrochloric acid were mixed and stirred, and the filtrate was added dropwise to the mixture while stirring, to obtain a precipitate. The precipitate was washed with water, filtered, and dried under reduced pressure at 40℃for 48 hours to give photosensitive disazo naphthoquinone (B-4).

Synthesis example 5

Synthesis of Compound B-5 having 1, 2-naphthoquinone diazide Structure

A photosensitive diazo naphthoquinone (B-5) was obtained by performing the reaction and purification in the same manner as in Synthesis example 4 except that 38.1g (0.141 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride was used instead of 38.1g (0.141 mol) of 1, 2-naphthoquinone diazide-4-sulfonyl chloride in Synthesis example 4.

Synthesis example 6

Synthesis of Compound B-6 having 1, 2-naphthoquinone diazide Structure

To a 1L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30g (0.0474 mol) of a compound represented by the following formula (29) (product name Tekoc-4HBPA, manufactured by Benzhou chemical industry Co., ltd.) as a hydroxyl compound was charged.

42.1g (0.155 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride in an amount equivalent to 80 mol% of the OH group of the hydroxyl compound was dissolved in 300g of acetone with stirring, and then added to a flask, and the flask was adjusted to 30℃with a constant temperature bath. Then, 15.4g of triethylamine was dissolved in 15g of acetone, and after being added to a dropping funnel, it was added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, stirring was continued for another 30 minutes, and then hydrochloric acid was added dropwise, followed by stirring for another 30 minutes, to complete the reaction. Thereafter, the reaction was filtered to remove triethylamine hydrochloride. In a 3L beaker, 1640g of pure water and 22g of hydrochloric acid were mixed and stirred, and the filtrate was added dropwise to the mixture while stirring, to obtain a precipitate. The precipitate was washed with water, filtered, and dried under reduced pressure at 40℃for 48 hours to give photosensitive disazo naphthoquinone (B-6).

Synthetic example 7

Synthesis of Compound B-7 having 1, 2-naphthoquinone diazide Structure

To a 1L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30g (0.131 mol) of a compound (2, 2-bis (4-hydroxyphenyl) propane) represented by the following formula (30) as a hydroxy compound was charged.

71.14g (0.263 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride in an amount equivalent to 100 mol% of the OH group of the hydroxyl compound was dissolved in 300g of acetone with stirring, and then added to a flask, and the flask was adjusted to 30℃with a constant temperature bath. Then, 26.6g of triethylamine was dissolved in 30g of acetone, and after being added to a dropping funnel, it was added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, stirring was continued for another 30 minutes, and then hydrochloric acid was added dropwise, followed by stirring for another 30 minutes, to complete the reaction. Thereafter, the reaction was filtered to remove triethylamine hydrochloride. In a 3L beaker, 1640g of pure water and 22g of hydrochloric acid were mixed and stirred, and the filtrate was added dropwise to the mixture while stirring, to obtain a precipitate. The precipitate was washed with water, filtered, and dried under reduced pressure at 40℃for 48 hours to give photosensitive diazo naphthoquinone (B-7).

Synthesis example 8

Synthesis of Compound B-8 having 1, 2-naphthoquinone diazide Structure

The reaction and purification were carried out in the same manner as described in Synthesis example 1 except that the amount of 1, 2-naphthoquinone diazide-5-sulfonyl chloride (53.56 g, 0.198 mol) in Synthesis example 1 was reduced to 47.82g (0.177 mol), to obtain photosensitive diazo naphthoquinone (B-8).

Synthetic example 9

Synthesis of Compound B-13 having 1, 2-naphthoquinone diazide Structure

To a 1L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30g (0.277 mol) of p-cresol, which is a compound represented by the following formula (31), was charged as a hydroxyl compound.

75.1g (0.277 mol) of 1, 2-naphthoquinone diazide-5-sulfonyl chloride in an amount equivalent to 100 mol% of the OH group of the hydroxyl compound was dissolved in 300g of acetone with stirring, and then added to a flask, and the flask was adjusted to 30℃with a constant temperature bath. Then, 28.1g of triethylamine was dissolved in 30g of acetone, and after being added to a dropping funnel, it was added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, stirring was continued for another 30 minutes, and then hydrochloric acid was added dropwise, followed by stirring for another 30 minutes, to complete the reaction. Thereafter, the reaction was filtered to remove triethylamine hydrochloride. 1600g of pure water and 22g of hydrochloric acid were mixed and stirred in a 3L beaker, and the filtrate was added dropwise to the mixture while stirring, to obtain a precipitate. The precipitate was washed with water, filtered, and dried under reduced pressure at 40℃for 48 hours to give photosensitive disazo naphthoquinone (B-13).

I. Examples 1 to 32 and comparative examples 1 to 26

Determination of the composition ratio of polyimide precursor resin composition

Example 1

The type of light used in the exposure is determined as i-rays. The resins shown in table 4 were selected as (a) polyimide precursor resins having absorbance parameters Xp in the range of 0.001 to 0.20. The compounds shown in table 4 were selected as the exposure light absorbers having absorbance parameters Xt in the range of 0.01 to 0.05. The compounds shown in Table 4 were selected as (C) photopolymerization initiators having absorbance parameters Xr in the range of 0 to 0.04. The assumed thickness D of the pre-baked film was set to 10 μm. Alpha, beta satisfying "0.7.ltoreq.Xp+Xt X alpha+Xr X beta). Times.D.ltoreq.2.2" was determined as the added mass part as described in Table 4. In this case, (xp+xt×α+xr×β) ×d is shown in table 5.

Examples 2 to 32

The composition ratio of the polyimide precursor resin composition was determined in the same manner as in example 1.

Preparation of polyimide precursor resin composition

Examples 1 to 32 and comparative examples 1 to 26

PI precursor resin compositions of examples 1 to 32 and comparative examples 1 to 26 were prepared by dissolving (a) a polyimide precursor resin, (B) an exposure light absorber, (C) a photopolymerization initiator, (E) a photopolymerizable compound, (F) a hindered phenol compound, and (G) a polymerization inhibitor in a mixed solvent composed of γ -butyrolactone and DMSO as solvents (weight ratio 80:20) in the compounding amounts shown in tables 4 and 6. The blending amounts in tables 4 and 6 are parts by mass of the respective components, assuming that the component (A) is 100 parts by mass. The viscosity of the resulting solution was adjusted to about 40 poise (poise) by further adding a small amount of the above mixed solvent, and filtration was performed with a polyethylene filter having a pore size of 0.2 μm to obtain a resin composition. The symbols in the table represent the following components, respectively.

As the polyimide precursor resin (A), the following (A-1) to (A-8) were used.

(A-1): the compound obtained in production example 1

(a-2): the compound obtained in production example 2

(A-3): the compound obtained in production example 3

(a-4): the compound obtained in production example 4

(A-5): the compound obtained in production example 5

(A-6): the compound obtained in production example 6

(A-7): the compound obtained in production example 7

(a-8): the compound obtained in production example 8

As the exposure light absorber (B), the following (B-1) to (B-11) were used.

(B-1): the diazonaphthoquinone compound obtained in Synthesis example 1

(B-2): the diazonaphthoquinone compound obtained in Synthesis example 2

(B-3): the diazonaphthoquinone compound obtained in Synthesis example 3

(B-4): the diazonaphthoquinone compound obtained in Synthesis example 4

(B-5): the diazonaphthoquinone compound obtained in Synthesis example 5

(B-6): the diazonaphthoquinone compound obtained in Synthesis example 6

(B-7): the diazonaphthoquinone compound obtained in Synthesis example 7

(B-8): the diazonaphthoquinone compound obtained in Synthesis example 8

(B-9): 2- (2H-Benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol (trade name: ADK STAB LA-29, manufactured by ADEKA, co., ltd.)

(B-10): 2,2', 4' -tetrahydroxybenzophenone (trade name: manufactured by SEESORB106, SHIPRO KASEI KAISHA, LTD.)

(B-11): curcumin (Tokyo chemical industry Co., ltd.)

(B-12): 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (trade name: JF-77, north chemical Co., ltd.)

(B-13): the diazonaphthoquinone compound obtained in Synthesis example 9

As the photopolymerization initiator (C), the following (C-1) to (C-4) were used.

(C-1): 1-phenyl-1, 2-propanedione-2- [ O- (ethoxycarbonyl) oxime ] (trade name: quantacure-PDO, manufactured by Japanese chemical Co., ltd.)

(C-2): 1, 2-octanedione-1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime) (trade name: IRGACURE-OXE-01, manufactured by BASF corporation)

(C-3): 1- [ 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation)

(C-4): n-phenylglycine (Tokyo chemical industry Co., ltd.)

As the photopolymerizable compound (E), the following (E-1) was used.

(E-1): tetraethylene glycol dimethacrylate (manufactured by tokyo chemical industry Co., ltd.)

In addition, the following components were used.

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

(G) 2-nitroso-1-naphthol

As the nitrogen-containing heterocyclic rust inhibitor (H), the following (H-1) to (H-2) were used.

(H-1): 8-azaadenine (Tokyo chemical industry Co., ltd.)

(H-2): 5-amino-1H-tetrazole (manufactured by Tokyo chemical industry Co., ltd.)

Determination of absorbance parameters

Determination of absorbance parameter Xp of polyimide precursor resin

The absorbance (absorbance parameter Xp) of A-1 to A-8 was measured under the following measurement conditions. A-1 to A-8 were dissolved in NMP at a concentration of 1000mg/L, respectively, to prepare measurement samples. The measurement device was a UV-visible spectrophotometer (manufactured by Shimadzu corporation) and a cuvette of 1cm was used for measurement. The value obtained by dividing the absorbance at 365nm of each sample by 10 was defined as Xp.

TABLE 1

Table 1.

	Xp
		A-1	0.028
A-2	O.016
		A-3	0.020
A-4	O.131
		A-5	0.060
A-6	0.194
		A-7	0.005
A-8	0.015

((B) determination of absorbance parameter Xt of exposure light absorber)

The absorbance (absorbance parameter Xt) of B1-B13 was measured by the following measurement conditions. Each of the components (B) was dissolved in NMP to adjust the concentration to 10mg/L, and the resulting solution was used as a measurement sample. The measurement device was a UV-visible spectrophotometer (UV-1800, manufactured by Shimadzu corporation) and a cuvette of 1cm was used for measurement. The value obtained by dividing the absorbance at 365nm of each sample by 10 was defined as Xt.

TABLE 2

	Xt
		B-1	0.021
B-2	0.019
		B-3	0.019
B-4	0.019
		B-5	0.018
B-6	0.019
		B-7	0.023
B-8	0.021
		B-9	0.023
B-10	0.040
		B-11	0.025
B-12	0.032
		B-13	0.028

((C) determination of absorbance parameter Xr of photopolymerization initiator)

The absorbance (absorbance parameter Xr) of C1-C-4 was measured by the following measurement conditions. Each of the components (C) was dissolved in NMP to adjust the concentration to 10mg/L, and the resulting solution was used as a measurement sample. The measurement device was a UV-visible spectrophotometer (UV-1800, manufactured by Shimadzu corporation) and a cuvette of 1cm was used for measurement. The absorbance at 365nm of each sample divided by 10 was defined as Xr.

TABLE 3

Table 3.

	Xr
		C-1	0.000
C-2	0.009
		C-3	0.009
C-4	0.001

Production and evaluation of relief Pattern film

A sputtering Cu wafer substrate was prepared by sequentially sputtering 200nm thick Ti and 400nm thick Cu on a 6 inch silicon wafer (manufactured by Fujimi Carbonisatus electric industries Co., ltd., thickness 625+25 μm) using a sputtering apparatus (manufactured by CANON ANELVA Co., ltd.). PI precursor resin composition was SPIN-coated on the above-mentioned sputtered Cu wafer substrate using a SPIN coater (model D-SPIN60A, manufactured by SOKUDO corporation) on a 6-inch silicon wafer, and dried at 100 ℃ for 180 seconds on a hot plate, thereby producing a pre-baked film having a thickness of 10.0 μm+0.2 μm (D'). A test pattern-carrying photomask having a pattern with a circular concave diameter of 10 μm was used to mount a gh ray cut filter on the spin coating film, from 30mJ/cm, using an equivalent projection exposure apparatus prism/N5503 (manufactured by Ultratech Co., ltd.) ² To 210mJ/cm ² At a rate of 15mJ/cm per time ² The exposure is performed by changing the exposure amount. Next, a coating film formed on the sputtered Cu wafer was subjected to spray development with a developing machine (D-SPIN 636, manufactured by japan corporation) using cyclopentanone, and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time of the spray development was defined as 1.4 times the minimum time for developing the resin composition in the unexposed portion of the 10.0 μm spin-coated film.

(evaluation of Cone shape of Pattern)

The cross section of the punched circular concave pattern having a diameter of 10 μm obtained as described above was cut by using a FIB device (JIB-4000, japan electronics), and the cross section shape of the pattern was observed, and the taper angle of the pattern with respect to the substrate was obtained by measuring the slope at the midpoint of the taper. The pattern cross-sectional shape was judged to be excellent (AA) when the taper angle was 70 ° to 80 °, the pattern was judged to be good (a) when the taper angle was 80 ° to 90 °, and the pattern was judged to be defective (D) when the taper angle was other than the taper angle. In addition, the pattern section was judged to be defective when undercut or bridging was observed. Fig. 1 shows FIB photographs of the cross-sectional shapes of the patterns obtained in example 1. In addition, an auxiliary line (1) showing the slope at the midpoint of the pattern is shown in fig. 1. The taper angle of the pattern obtained in example 1 was 82 ° with respect to the substrate (auxiliary line (2)). In the taper shape evaluation, the pattern shape failure person did not perform the highest resolution evaluation and sensitivity acceptability evaluation described below.

Evaluation of highest resolution

According to the above description, the diameter of the punched circular concave pattern was changed, and the minimum value of the mask size of the obtained punched circular concave relief pattern was set to the highest resolution (μm), and the evaluation was performed according to the following criteria.

A: pattern openings of less than 5 μm

B: pattern openings of 5 μm or more and less than 6 μm

C: pattern openings of 6 μm or more and less than 8 μm

D: pattern non-openings smaller than 8 μm

Whether or not the punched circular concave relief pattern is open is determined to be acceptable by satisfying the following criteria (I) and (II).

(I) The area of the pattern opening is more than 1/2 of the corresponding pattern mask opening area.

And (II) the pattern section is not turned up, undercut, swelling and bridging.

Assessment of sensitivity acceptability

The range of exposure to an opening having a diameter of 8 μm was confirmed in the punched circular concave relief pattern obtained as described above according to the following standard evaluation.

A：For a pattern of 8 μm, 105mJ/cm ² The exposure magnitude realizes the opening

B: for a pattern of 8 μm, 45mJ/cm ² Above and less than 105mJ/cm ² Exposure magnitude realization aperture of (a)

C: for a pattern of 8 μm, 15mJ/cm ² Above and below 45mJ/cm ² Exposure magnitude realization aperture of (a)

D: for a pattern of 8 μm, the openings are needle points or no openings

TABLE 4

Table 4.

TABLE 5

Table 5.

TABLE 6

Table 6.

TABLE 7

Table 7.

II. examples 33 to 49 and comparative examples 27 to 40

Determination of the composition ratio of polyimide precursor resin composition

Example 33

The type of light used in the exposure is determined as i-rays. The resins shown in table 8 were selected as (a) polyimide precursor resins having absorbance parameters Xp in the range of 0.001 to 0.20. The compounds shown in table 8 were selected as the exposure light absorbers having absorbance parameters Xt in the range of 0.01 to 0.05. The compounds shown in Table 8 were selected as (C) photopolymerization initiators having absorbance parameters Xr in the range of 0 to 0.04. The assumed thickness D of the pre-baked film was set to 5 μm. Alpha, beta satisfying "0.7.ltoreq.Xp+Xt X alpha+Xr X beta). Times.D.ltoreq.2.2" was determined as the added mass part as described in Table 8. In this case, (xp+xt×α+xr×β) ×d is shown in table 9.

Examples 34 to 49

The composition ratio of the polyimide precursor resin composition was determined in the same manner as in example 33.

Preparation of polyimide precursor resin composition

Examples 33 to 49 and comparative examples 27 to 40

The PI precursor resin compositions of examples 33 to 49 and comparative examples 27 to 40 were prepared by dissolving (a) a polyimide precursor resin, (B) an exposure light absorber, (C) a photopolymerization initiator, (E) a photopolymerizable compound, (F) a hindered phenol compound, and (G) a polymerization inhibitor in a mixed solvent composed of γ -butyrolactone and DMSO as the solvent (weight ratio of 80:20) in the compounding amounts shown in tables 8 and 10. The blending amounts in tables 8 and 10 are parts by mass of the respective components, assuming that the component (A) is 100 parts by mass. The viscosity of the resulting solution was adjusted to about 15 poise (poise) by further adding a small amount of the above mixed solvent, and filtration was performed with a polyethylene filter having a pore size of 0.2 μm to obtain a resin composition.

Production and evaluation of relief Pattern film

A sputtering Cu wafer substrate was prepared by sequentially sputtering 200nm thick Ti and 400nm thick Cu on a 6-inch silicon wafer (manufactured by Fujimi Carbonisatus electronic industries Co., ltd., thickness 625.+ -. 25 μm) using a sputtering apparatus (manufactured by CANON ANELVA Co., ltd.). The PI precursor resin composition was SPIN-coated on the above-mentioned sputtered Cu wafer substrate using a SPIN coater (model D-SPIN60A, manufactured by SOKUDO corporation) on a 6-inch silicon wafer, and dried at 100 ℃ for 180 seconds on a hot plate, thereby producing a coating film having a thickness of 5 μm±0.2 μm (D'). On the spin-coated film, a Reticle (Reticle) with a test pattern having a punched circular concave pattern with a diameter of 5 μm was used, and an equivalent projection exposure apparatus was used PrsmaGHI S/N5503 (manufactured by Ultratech Co.) is equipped with a gh ray cut filter at a rate of 30mJ/cm ² To 150mJ/cm ² At a rate of 10mJ/cm each time ² The exposure is performed by changing the exposure amount. Next, a coating film formed on the sputtered Cu wafer was subjected to spray development with a developing machine (D-SPIN 636, manufactured by japan) using cyclopentanone, and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time of the spray development was defined as 1.4 times the minimum time for developing the resin composition in the unexposed portion of the spin-coated film of 5.0. Mu.m.

Cone shape evaluation of Pattern

The cross section of the punched circular concave pattern having a diameter of 5 μm obtained as described above was cut by using a FIB device (JIB-4000, japan electronics), and the cross section shape of the pattern was observed, and the taper angle of the pattern with respect to the substrate was obtained by measuring the slope at the midpoint of the taper. The pattern cross-sectional shape was judged to be excellent (AA) when the taper angle was 70 ° to 80 °, the pattern was judged to be good (a) when the taper angle was 80 ° to 90 °, and the pattern was judged to be defective (D) when the taper angle was other than the taper angle. In addition, the pattern section was judged to be defective when undercut or bridging was observed. In the taper shape evaluation, the pattern shape failure person did not perform the highest resolution evaluation and sensitivity acceptability evaluation described below.

Evaluation of highest resolution

A: pattern openings smaller than 3.5 μm

B: pattern openings of 3.5 μm or more and less than 4.5 μm

C: pattern openings of 4.5 μm or more and less than 6 μm

D: pattern non-openings smaller than 6 μm

And (II) the pattern section is not turned up, undercut, swelling and bridging.

Assessment of sensitivity acceptability

A: for a pattern of 5 μm, 30mJ/cm ² The exposure magnitude realizes the opening

B: for a pattern of 5 μm, at 20mJ/cm ² Above and below 30mJ/cm ² Exposure magnitude realization aperture of (a)

C: for a pattern of 5 μm, at 10mJ/cm ² Above and below 20mJ/cm ² Exposure magnitude realization aperture of (a)

D: for a pattern of 5 μm, the openings are needle points or no openings

TABLE 8

Table 8.

TABLE 9

Table 9.

TABLE 10

Table 10.

TABLE 11

Table 11.

III. examples 50 to 65 and comparative examples 41 to 44

Determination of the composition ratio of polyimide precursor resin composition

Examples 50 to 65

Preparation of polyimide precursor resin composition

Examples 50 to 65 and comparative examples 41 to 44

The PI precursor resin compositions of examples 50 to 65 and comparative examples 41 to 44 were prepared by dissolving (a) a polyimide precursor resin, (B) an exposure light absorber, (C) a photopolymerization initiator, (E) a photopolymerizable compound, (F) a hindered phenol compound, (G) a polymerization inhibitor, and (H) a nitrogen-containing heterocyclic rust inhibitor in a mixed solvent (weight ratio of 80:20) composed of γ -butyrolactone and DMSO as the solvent (D) in the compounding amounts shown in the table. The blending amount in the table is the mass parts of each component, assuming that the component (A) is 100 mass parts. The viscosity of the resulting solution was adjusted to about 40 poise (poise) by further adding a small amount of the above mixed solvent, and filtration was performed with a polyethylene filter having a pore size of 0.2 μm to obtain a resin composition.

Production and evaluation of relief Pattern film

Using the obtained polyimide precursor resin compositions, embossed pattern films were produced in the same manner as in examples 1 to 32 and comparative examples 1 to 26.

Cone shape evaluation of Pattern

The cone shape of the obtained relief pattern films was evaluated in the same manner as in examples 1 to 32 and comparative examples 1 to 26.

Evaluation of highest resolution

The resolution of the obtained relief pattern films was evaluated in the same manner as in examples 1 to 32 and comparative examples 1 to 26.

Assessment of sensitivity acceptability

The sensitivity acceptability of the obtained relief pattern films was evaluated in the same manner as in examples 1 to 32 and comparative examples 1 to 26.

Evaluation of storage stability

The photosensitive resin composition was initially prepared after stirring at room temperature (23.0.+ -. 0.5 ℃ C., relative humidity 50%.+ -. 10%) for 3 days, and then allowed to stand at room temperature for 4 weeks. The PI precursor resin composition in the initial state was SPIN-coated on a 6-inch silicon wafer (thickness 625±25 μm, manufactured by fogimi electronics corporation) using a SPIN coater (manufactured by D-SPIN60A, manufactured by SOKUDO corporation), and dried on a hot plate at 100 ℃ for 180 seconds, thereby producing a pre-baked film having a thickness of 10.0 μm±0.2 μm (D'). A test pattern-carrying photomask having a pattern with a punched circular concave shape having a diameter of 10 μm was used to mount a gh ray cut filter on the spin coating film from 30mJ/cm using an equivalent projection exposure apparatus prism (manufactured by Ultratech Co.) S/N5503 ² To 270mJ/cm ² At 20mJ/cm each time ² The exposure is performed by changing the exposure amount. Next, a coating film formed on the wafer was subjected to spray development with a developing machine (D-SPIN 636, manufactured by japan s) using cyclopentanone, and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time of the spray development was defined as 1.4 times the minimum time for developing the resin composition in the unexposed portion of the 10.0 μm spin-coated film. The film thickness of the relief pattern obtained in example 50 was measured at each exposure amount. An example of the resulting sensitivity curve is shown in fig. 2. Here, the vertical axis shows the relative film thickness (Normalized film thickness) as (film thickness after Exposure development/film thickness before Exposure) ×100 (%), and the horizontal axis shows the Exposure dose (Exposure dose). The exposure amount at the portion where the relative film thickness (Normalized film thickness) reached about 85% was defined as the sensitivity exposure amount (mJ/cm) ² )。

Next, a relief pattern film was produced by spin coating, exposure and development under the same conditions as in the case of the PI precursor resin composition in the initial state, with respect to the PI precursor resin composition left standing at room temperature for 4 weeks, and the relative film thickness was calculated similarly (Normalized film thickness). The storage stability was evaluated based on the amount of change in the relative film thickness with time at the sensitivity exposure amount set by the PI precursor resin evaluation in the initial state, according to the following criteria. For example, the relative film thickness variation with time of fig. 2 is 1.3%.

A: the amount of change in the relative film thickness with time is less than 0 to + -2%.

B: the amount of change in the relative film thickness over time is + -2% or more.

In tables 13 and 15, the values of the relative film thickness of the PI precursor resin composition after 4 weeks of standing, which are higher than the relative film thickness of the PI precursor resin composition in the initial state, are shown in the positive (+) column, and the values of the PI precursor resin composition in the initial state, which are lower than the relative film thickness, are shown in the negative (-) column.

TABLE 12

Table 12.

TABLE 13

Table 13.

TABLE 14

Table 14.

TABLE 15

Table 15.

IV. examples 66 to 78 and comparative examples 45 to 47

Determination of the composition ratio of polyimide precursor resin composition

Examples 66 to 78

Preparation of polyimide precursor resin composition

Examples 66 to 78 and comparative examples 45 to 47

The PI precursor resin compositions of examples 66 to 78 and comparative examples 45 to 47 were prepared by dissolving (a) a polyimide precursor resin, (B) an exposure light absorber, (C) a photopolymerization initiator, (E) a photopolymerizable compound, (F) a hindered phenol compound, (G) a polymerization inhibitor, and (H) a nitrogen-containing heterocyclic rust inhibitor in a mixed solvent (weight ratio of 80:20) composed of γ -butyrolactone and DMSO as the solvent according to the compounding amounts shown in the table. The blending amount in the table is the mass parts of each component, assuming that the component (A) is 100 mass parts. The viscosity of the resulting solution was adjusted to about 15 poise (poise) by further adding a small amount of the above mixed solvent, and filtration was performed with a polyethylene filter having a pore size of 0.2 μm to obtain a resin composition. The symbols in the table represent the above components, respectively.

Production and evaluation of relief Pattern film

Using the obtained polyimide precursor resin compositions, embossed pattern films were produced in the same manner as in examples 33 to 49 and comparative examples 27 to 40.

Cone shape evaluation of Pattern

The cone shape of the obtained relief pattern films was evaluated in the same manner as in examples 33 to 49 and comparative examples 27 to 40.

Evaluation of highest resolution

The resolution of the obtained relief pattern films was evaluated in the same manner as in examples 33 to 49 and comparative examples 27 to 40.

Assessment of sensitivity acceptability

The sensitivity acceptability of the obtained relief pattern films was evaluated in the same manner as in examples 33 to 49 and comparative examples 27 to 40.

Evaluation of storage stability

The photosensitive resin composition was initially prepared after stirring at room temperature (23.0.+ -. 0.5 ℃ C., relative humidity 50%.+ -. 10%) for 3 days, and then allowed to stand at room temperature for 4 weeks. Will be in an initial stateThe PI precursor resin composition was SPIN-coated on a 6-inch silicon wafer (thickness 625±25 μm, manufactured by fogimi electronics corporation) using a SPIN coater (model D-SPIN60A, manufactured by SOKUDO corporation), and dried on a hot plate at 100 ℃ for 180 seconds, thereby producing a pre-baked film having a thickness of 5.0 μm±0.2 μm (D'). A test pattern-carrying photomask having a pattern with a punched circular concave shape having a diameter of 10 μm was used to mount a gh ray cut filter on the spin coating film from 30mJ/cm using an equivalent projection exposure apparatus prism (manufactured by Ultratech Co.) S/N5503 ² To 150mJ/cm ² At a rate of 10mJ/cm each time ² The exposure is performed by changing the exposure amount. Next, a coating film formed on the wafer was subjected to spray development with a developing machine (D-SPIN 636, manufactured by japan s) using cyclopentanone, and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time of the spray development was defined as 1.4 times the minimum time for developing the resin composition in the unexposed portion of the spin-coated film of 5.0. Mu.m. For the obtained relief pattern, a relative film thickness (Normalized film thickness) was calculated, and the exposure amount at a portion where the relative film thickness reached about 80% was defined as a sensitivity exposure amount (mJ/cm) ² )。

Next, the PI precursor resin composition was left to stand at room temperature for 4 weeks, and was spin-coated, exposed and developed under the same conditions as in the case of the PI precursor resin composition in the initial state, and the storage stability was evaluated based on the amount of change in relative film thickness with time at the sensitivity exposure amount, according to the following criteria.

In tables 17 and 19, the values of the relative film thickness of the PI precursor resin composition after 4 weeks of standing, which are higher than the relative film thickness of the PI precursor resin composition in the initial state, are shown in the positive (+) column, and the values of the PI precursor resin composition in the initial state, which are lower than the relative film thickness, are shown in the negative (-) column.

TABLE 16

Table 16.

TABLE 17

Table 17.

TABLE 18

Table 18.

TABLE 19

Table 19.

As is clear from the results of tables 4 to 19 above, in the examples, the highest resolution and sensitivity acceptability were improved relative to the comparative examples by including the PI precursor resin composition with the exposure light absorber. As is clear from tables 12 to 19, in the examples including both the exposure light absorber and the nitrogen-containing heterocyclic rust inhibitor, the storage stability test result was a determination, and the storage stability was significantly improved by the combination of both, compared with the composition containing only one.

Industrial applicability

According to the present disclosure, by adjusting the light transmittance of the entire resin composition using the light (i-ray) absorbing function of the exposure light absorber, it is possible to provide a pattern cured film excellent in resolution and handleability, and a method for forming a cured relief pattern using the PI precursor resin composition. The present disclosure can be suitably used in the field of photosensitive materials useful in the production of electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. a manufacture method of PI precursor resin composition, it is the manufacture method of the PI precursor resin composition containing polyimide (PI) precursor resin, exposure light absorber, photopolymerization initiator and solvent, The manufacturing method includes:

the process of determining the type of light to be used in the exposure;

Select the PI precursor resin from resins whose absorbance parameter Xp for the determined light type is in the range of 0.001-0.20, and select the PI precursor resin from materials whose absorbance parameter Xt for the determined light type is in the range of 0.01-0.05. The process of exposing the light absorber and selecting the photopolymerization initiator from materials whose absorbance parameter Xr for the determined light type is in the range of 0 to 0.04;

Based on the selected absorbance parameter Xp of the PI precursor resin, the selected absorbance parameter Xt of the exposure light absorber, the selected absorbance parameter Xr of the photopolymerization initiator and the PI precursor resin The envisaged thickness D of the pre-baked film formed by coating the composition and desolventizing it, so as to satisfy the following formula to determine the addition of the exposure light absorber based on 100 parts by mass of the PI precursor resin a step of adding parts by mass α and the photopolymerization initiator to parts by mass β,

0.7≤(Xp+Xt×α+Xr×β)×D≤2.2; and

The PI precursor resin is prepared in a manner including the determined PI precursor resin, the determined added mass part α of the exposure light absorber, the determined added mass part β of the photopolymerization initiator and a solvent composition process.

2. manufacturing method according to claim 1, wherein, described PI precursor resin has the structural unit shown in following formula (1),

In formula (1), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom, or the following A monovalent organic group represented by general formula (2), or a saturated aliphatic group with 1 to 4 carbon atoms,

In formula (2), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbons, and m ₁ is an integer of 2 to 10.

3. The manufacturing method according to claim 1 or 2, wherein the type of light used in the exposure is i-ray.

4. The manufacturing method according to any one of claims 1 to 3, wherein the added mass part α of the exposure light absorber and the light The addition mass part β of the polymerization initiator.

5. The manufacturing method according to any one of claims 1 to 4, wherein the photopolymerization initiator has an oxime ester structure represented by the following general formula (5),

In the formula (5), R ₁₆ , R ₁₇ and R ₁₈ are each a monovalent organic group, and R ₁₆ and R ₁₇ are optionally connected to each other to form a ring structure.

6. The manufacturing method according to any one of claims 1 to 5, wherein the PI precursor resin composition further comprises a nitrogen-containing heterocyclic ring antirust agent.

7. The production method according to any one of claims 1 to 6, wherein the exposure light absorber is a compound having a 1,2-naphthoquinonediazide structure.

8. The manufacturing method according to any one of claims 1 to 7, wherein the PI precursor resin composition further contains a photopolymerizable compound.

9. The production method according to any one of claims 1 to 8, wherein _Y of the formula (1) is a divalent organic group represented by the following formula (3),

In formula (3), R ₆ to R ₁₃ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ₆ to R ₁₃ is methyl, trifluoromethyl or methoxy .

10. The production method according to any one of claims 1 to 9, wherein Y of the formula ( ₁ ) is a divalent organic group represented by the following formula (4),

In formula (4), R ₁₄ and R ₁₅ are each independently methyl, trifluoromethyl or methoxy.

11. The production method according to any one of claims 1 to 10, wherein the exposure light absorber is at least one hydroxyl compound selected from the group consisting of the following general formulas (6) to (10) 1,2-Naphthoquinonediazide-4-sulfonate and/or 1,2-Naphthoquinonediazide-5-sulfonate,

In formula (6), _X1 and _X2 each independently represent a hydrogen atom or a monovalent organic group with 1 to 60 carbons, and _X3 and _X4 each independently represent a hydrogen atom or a 1 to 60 carbon number A valent organic group, r1, r2, r3 and r4 are each independently an integer of 0 to 5, at least one of r3 and r4 is an integer of 1 to 5, r1+r3=5, and r2+r4=5 ,

In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms, X ₅ , X ₆ , X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 30 carbon atoms, r6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, r10, r11, r12 and r13 are each independently an integer of 0 to 2, and among r10, r11, r12 and r13 at least 1 of is 1 or 2,

In formula (8), r14 represents an integer of 1 to 5, r15 is an integer of 3 to 8, r14×r15 Ls each independently represent a monovalent organic group with a carbon number of 1 to 20, and r15 Ts each independently Represents a hydrogen atom or a monovalent organic group with 1 to 20 carbons, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group with 1 to 20 carbons,

In the formula (9), A represents a divalent organic group containing aliphatic tertiary carbon or quaternary carbon, and M represents a divalent organic group,

In formula (10), r17, r18, r19, and r20 are each independently an integer of 0 to 2, at least one of r17, r18, r19, and r20 is 1 or 2, and X ₁₀ to X ₁₉ independently represent the selected At least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y ₁ to Y ₃ each independently represent a group selected from a single bond , -O-, -S-, -SO-, -SO ₂ -, -CO-, -CO ₂ -, cyclopentylene, cyclohexylene, phenylene and divalent organic compounds with 1 to 20 carbon atoms At least one divalent group in the group consisting of groups.

12. The production method according to any one of claims 1 to 11, wherein the exposure light absorber is 1 of at least one hydroxyl compound selected from the group consisting of the formulas (6) to (10). ,2-Naphthoquinonediazide-5-sulfonate.

13. The production method according to any one of claims 1 to 12, wherein the esterification rate of the exposure light absorber is 80% or more.

14. The production method according to any one of claims 1 to 13, wherein the hydroxy compound represented by the general formula (6) is represented by the following general formula (11),

In formula (11), r20 are each independently an integer of 0 to 2, and _X9 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

15. A method of manufacturing a relief pattern film, the method comprising:

The process of manufacturing the PI precursor resin composition containing PI precursor resin, exposure light absorber, photopolymerization initiator and solvent by the method described in any one of claims 1 to 14;

Coating process, obtain the coating film of described PI precursor resin composition;

Drying process, desolventizing the solvent in the coating film to obtain a photosensitive resin layer with a thickness D';

an exposing step of exposing the photosensitive resin layer by the determined light type; and

In the development step, after the exposure, the photosensitive resin layer is developed to obtain a relief pattern film.

16. the manufacture method of relief pattern film according to claim 15, wherein, the coating film that the thickness after desolvation is D ' is:

0.7≤(Xp+Xt×α+Xr×β)×D'≤2.2.

17. A PI precursor resin composition, which contains PI precursor resin, based on 100 parts by mass of the PI precursor resin, an exposure light absorber whose mass part is α, and a photopolymerization initiator whose mass part is β and solvents,

The absorbance parameter Xp of the PI precursor resin to i-ray,

The absorbance parameter Xt of the exposure light absorber to i-ray,

The absorbance parameter Xr of the photopolymerization initiator of i-ray,

The mass parts α of the exposure light absorber, and

The relation of the mass parts β of described photopolymerization initiator is:

0.7≤(Xp+Xt×α+Xr×β)×10≤2.2

0.001≤Xp≤0.20

0.01≤Xt≤0.05

0≤Xr≤0.04.

18. A PI precursor resin composition, which contains polyimide (PI) precursor resin, 100 mass parts of said PI precursor resin as a basis for mass parts of the exposure light absorber, mass parts are β photopolymerization initiator and solvent,

The absorbance parameter Xp of the PI precursor resin to i-ray,

The absorbance parameter Xt of the exposure light absorber to i-ray,

The absorbance parameter Xr of the photopolymerization initiator of i-ray,

The mass parts α of the exposure light absorber, and

0.7≤(Xp+Xt×α+Xr×β)×5≤2.2

0.001≤Xp≤0.20

0.01≤Xt≤0.05

0≤Xr≤0.04.

19. The PI precursor resin composition according to claim 17 or 18, wherein, the PI precursor resin has a structural unit shown in the following formula (1),

20. The PI precursor resin composition according to any one of claims 17 to 19, wherein the photopolymerization initiator has an oxime ester structure represented by the following general formula (5),

21. The PI precursor resin composition according to any one of claims 17 to 20, wherein the PI precursor resin composition further comprises a nitrogen-containing heterocyclic ring antirust agent.

22. The PI precursor resin composition according to any one of claims 17 to 21, wherein the exposure light absorber is a compound having a 1,2-naphthoquinonediazide structure.

23. The PI precursor resin composition according to any one of claims 17 to 22, wherein the PI precursor resin composition further contains a photopolymerizable compound.

24. The PI precursor resin composition according to any one of claims 17 to 23, wherein _Y of the formula (1) is a divalent organic group represented by the following formula (3),

25. The PI precursor resin composition according to any one of claims 17 to 24, wherein Y of the formula ( ₁ ) is a divalent organic group represented by the following formula (4),

26. The PI precursor resin composition according to any one of claims 17 to 25, wherein the exposure light absorber is at least one selected from the group consisting of the following general formulas (6) to (10). 1,2-Naphthoquinonediazide-4-sulfonate and/or 1,2-Naphthoquinonediazide-5-sulfonate of a hydroxy compound,

27. The PI precursor resin composition according to any one of claims 17 to 26, wherein the exposure light absorber is at least one selected from the group consisting of the formulas (6) to (10) 1,2-Naphthoquinonediazide-5-sulfonate of hydroxy compounds.

28. The PI precursor resin composition according to any one of claims 17 to 27, wherein the esterification rate of the exposure light absorber is 80% or more.

29. The PI precursor resin composition according to any one of claims 17 to 28, wherein the hydroxyl compound represented by the general formula (6) is represented by the following general formula (11),

In the formula (11), r16 are each independently an integer of 0 to 2, and _X9 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

30. A cured film of the PI precursor resin composition according to any one of claims 17 to 29.

31. A prebaked film whose thickness D' is 1 μm≤D'≤20 μm,

The prebaked film contains a polyimide (PI) precursor resin, α parts by mass of the exposure light absorber relative to 100 parts by mass of the PI precursor resin, and 100 parts by mass of the PI precursor resin. The photopolymerization initiator whose mass parts are β mass parts,

The absorbance parameter Xp of the PI precursor resin to i-ray is in the range of 0.001≤Xp≤0.20,

The absorbance parameter Xt of the exposure light absorber to i-ray is in the range of 0.01≤Xt≤0.05,

The absorbance parameter Xr of the photopolymerization initiator to i-ray is in the range of 0≤Xr≤0.04,

The prebaked film satisfies the following formula:

0.7≤(Xp+Xt×α+Xr×β)×D'≤2.2.

32. The prebaked film according to claim 31, wherein the PI precursor resin has a structural unit represented by the following formula (1),

33. The prebaked film according to claim 31 or 32, wherein the thickness D' of the prebaked film is 1 μm≤D'<7 μm.

34. The prebaked film according to any one of claims 31 to 33, wherein the photopolymerization initiator has an oxime ester structure represented by the following general formula (5),

35. The prebaked film according to any one of claims 31 to 34, wherein the prebaked film further comprises a nitrogen-containing heterocyclic antirust agent.

36. The prebaked film according to any one of claims 31 to 35, wherein the exposure light absorber is a compound having a 1,2-naphthoquinonediazide structure.

37. The prebaked film according to any one of claims 31 to 36, further comprising a photopolymerizable compound.

38. The prebaked film according to any one of claims 31 to 37, wherein Y in the formula (1) is a divalent organic group _shown in the following formula (3),

39. The prebaked film according to any one of claims 31 to 38, wherein Y in the formula ( ₁ ) is a divalent organic group shown in the following formula (4),

40. The prebaked film according to any one of claims 31 to 39, wherein the exposure light absorber is at least one selected from the group consisting of the following general formulas (6) to (10): 1,2-Naphthoquinonediazide-4-sulfonate and/or 1,2-Naphthoquinonediazide-5-sulfonate of hydroxy compounds,

41. The prebaked film according to any one of claims 31 to 40, wherein the exposure light absorber is at least one hydroxyl compound selected from the group consisting of the formulas (6) to (10) 1,2-Naphthoquinonediazide-5-sulfonate.

42. The prebaked film according to any one of claims 31 to 41, wherein the esterification rate of the exposure light absorber is 80% or more.

43. The prebaked film according to any one of claims 31 to 42, wherein the hydroxy compound represented by the general formula (6) is represented by the following general formula (11),