WO2019107250A1

WO2019107250A1 - Negative photosensitive resin composition, method for producing said composition, and method for producing cured relief pattern

Info

Publication number: WO2019107250A1
Application number: PCT/JP2018/043050
Authority: WO
Inventors: 秀二郎塩崎; 竜也平田
Original assignee: 旭化成株式会社
Priority date: 2017-11-28
Filing date: 2018-11-21
Publication date: 2019-06-06
Also published as: JP7393491B2; KR102402138B1; KR20200044927A; JP6968196B2; JP2021131543A; TW201925918A; TWI700554B; JP7146014B2; JPWO2019107250A1; JP2022173316A

Abstract

The present invention provides: a negative photosensitive resin composition that achieves a high resolution, and suppresses the occurrence of voids at an interface of a Cu layer contacting a resin layer after a high-temperature storage test; a method for producing said composition; and a method for forming a cured relief pattern. This negative photosensitive resin composition comprises: (A) a polyimide precursor; (B) a base protected compound; and (C) a photopolymerisation initiator. The base protected compound: comprises multiple amino groups protected by a group which is deprotected by an acid, a base or heat; has a molecular weight of 250–600; the protected multiple amino groups are aliphatic-chain or alicyclic amino groups; and has a solubility parameter value of 20.0–24.0.

Description

Negative photosensitive resin composition, method for producing the same, and method for producing a cured relief pattern

The present invention relates to a negative photosensitive resin composition, a method for producing the same, and a method for producing a cured relief pattern.

Conventionally, polyimide resins, polybenzoxazole resins, phenol resins, etc. having excellent heat resistance, electrical properties and mechanical properties are used for insulating materials of electronic parts, passivation films, surface protective films, interlayer insulating films etc. of semiconductor devices. It is used. Among these resins, those provided in the form of a photosensitive resin composition easily form a heat-resistant relief pattern film by thermal imidization treatment by application, exposure, development, and curing of the composition. be able to. Such a photosensitive resin composition has a feature of enabling significant process reduction as compared to conventional non-photosensitive materials.

By the way, a semiconductor device (hereinafter, also referred to as “element”) is mounted on a printed circuit board by various methods according to the purpose. Conventional devices are generally manufactured by a wire bonding method in which thin wires are connected from the external terminals (pads) of the devices to the lead frame. However, as the speed of elements has been increased and the operating frequency has reached GHz, the difference in wiring length of each terminal in mounting has come to affect the operation of the elements. Therefore, in the case of the mounting of elements for high-end applications, it becomes necessary to control the length of the mounting wiring accurately, and it has become difficult to meet the requirement in the wire bonding.

Therefore, there has been proposed flip chip mounting in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, the chip is turned over, and the chip is directly mounted on a printed board (for example, patent) Reference 1). In this flip-chip mounting, since the wiring distance can be accurately controlled, the demand is rapidly expanding, being adopted for high-end devices that handle high-speed signals, or for small size due to small mounting size. When a material such as polyimide, polybenzoxazole, or phenol resin is used for flip chip mounting, a metal wiring layer formation step is performed after a pattern of the resin layer is formed. The metal wiring layer is generally plasma etched on the surface of the resin layer to roughen the surface, then a metal layer to be a seed layer for plating is formed by sputtering with a thickness of 1 μm or less, and the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, titanium (Ti) is generally used as a metal to be a seed layer, and copper (Cu) is used as a metal of a redistribution layer formed by electrolytic plating.

Such a metal redistribution layer is required to have high adhesion between the metal layer re-wired after the reliability test and the resin layer. As a reliability test, for example, high temperature storage test stored in air at a high temperature of 125 ° C. or more for 100 hours or more; a wiring is conducted while applying a voltage, in air, at a temperature of about 125 ° C. for 100 hours or more High temperature operation test to confirm the operation under storage over temperature; temperature cycle in which the low temperature condition of about -65 ° C to -40 ° C and the high temperature condition of about 125 ° C to 150 ° C are cycled in air Test: store at 85 ° C or higher in a water vapor atmosphere with a humidity of 85% or higher, high temperature and high humidity storage test; perform the same test as high temperature and high humidity storage test while applying voltage while forming wiring, high temperature and high humidity Bias test; and solder reflow test which passes through a solder reflow furnace at 260 ° C. in air or under nitrogen a plurality of times can be mentioned.

JP, 2001-338947, A

However, conventionally, in the case of the high temperature storage test in the above-mentioned reliability test, there has been a problem that a void is generated at the interface of the Cu layer rewired after the test in contact with the resin layer. If a void is generated at the interface between the Cu layer and the resin layer, the adhesion between the two will be reduced.

In addition to the problem of voids, the demand for finer metal redistribution layers (hardened relief patterns) is also increasing. For this reason, it is required that the photosensitive resin composition used particularly for the formation of the semiconductor metal rewiring layer has high resolution while suppressing the occurrence of voids. In one embodiment, the metal redistribution layer is required to have high chemical resistance.

The present invention was devised in view of such conventional circumstances, and high resolution is obtained, and after a high temperature storage test, voids in the interface of the Cu layer in contact with the resin layer are obtained. An object of the present invention is to provide a negative photosensitive resin composition (hereinafter, also simply referred to as "photosensitive resin composition" in the present specification) capable of suppressing the generation and a method for producing the same. It is also an object to provide a method for forming a cured relief pattern using the negative photosensitive resin composition of the present invention. In one embodiment, a negative photosensitive resin composition having high chemical resistance, high resolution, and high void suppression effect, a method for producing the same, and a cured relief pattern using the negative photosensitive resin composition It is an object to provide a formation method.

The present inventors solve the above problems by combining a polyimide precursor and a photopolymerization initiator with a specific compound having an acid or base or an amino group protected by a thermally deprotected group. It has been found that the present invention can be accomplished. Examples of embodiments of the present invention are listed below.
[1]
(A) polyimide precursor;
(B) A plurality of amino groups protected by an acid or a base or a group to be deprotected by heat, having a molecular weight of 250 to 600, and the plurality of protected amino groups having an aliphatic chain or alicyclic structure A negative photosensitive resin composition comprising a base-protected compound which is an amino group of the formula and has a solubility parameter value of 20.0 to 24.0; and (C) a photopolymerization initiator.
[2]
The negative photosensitive resin composition according to item 1, wherein the plurality of protected amino groups are amino groups protected by a tert-butoxycarbonyl group.
[3]
The (A) polyimide precursor is represented by the following general formula (2):

Wherein 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 hydrogen It is an atom or a monovalent organic group, and at least one of R ₁ and R ₂ is a monovalent organic group having a polymerizable group at its end. }
The negative photosensitive resin composition as described in any one of claim | item 1 or 2 containing the polyimide precursor which has a structural unit represented by these.
[4]
In the general formula (2), at least one of R ₁ and R ₂ has the following general formula (3):

Wherein L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. The negative photosensitive resin composition according to Item 3, which is a monovalent organic group represented by
[5]
The (A) polyimide precursor is represented by the following general formula (4):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
5. The negative photosensitive resin composition according to item 3 or 4, comprising a polyimide precursor having a structural unit represented by
[6]
The (A) polyimide precursor is represented by the following general formula (5):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
5. The negative photosensitive resin composition according to item 3 or 4, comprising a polyimide precursor having a structural unit represented by
[7]
The (A) polyimide precursor is represented by the following general formula (6):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
5. The negative photosensitive resin composition according to item 3 or 4, comprising a polyimide precursor having a structural unit represented by
[8]
The (A) polyimide precursor is represented by the following general formula (4):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{Wherein R ₁ , R ₂ and n ₁ are as defined in the above general formula (2), provided that R ₁ , R ₂ and n ₁ in the general formula (5) are 4) R ₁ , R ₂ and n _{1 in} 4) are independently selected. }
5. The negative photosensitive resin composition according to item 3 or 4, which comprises both of the polyimide precursors having a structural unit represented by
[9]
The (A) polyimide precursor is represented by the following general formula (4):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by the following general formula (6):

{Wherein R ₁ , R ₂ and n ₁ are as defined in the above general formula (2), provided that R ₁ , R ₂ and n ₁ in the general formula (6) are 4) R ₁ , R ₂ and n _{1 in} 4) are independently selected. }
5. The negative photosensitive resin composition according to item 3 or 4, which comprises both of the polyimide precursors having a structural unit represented by
[10]
100 parts by mass of the above (A) polyimide precursor
0.1 to 30 parts by mass of the above base protection compound (B) with respect to 100 parts by mass of the above (A) polyimide precursor,
The negative photosensitive resin according to any one of items 1 to 9, comprising 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor Composition.
[11]
(A) polyimide precursor;
(D) One or more amino groups protected by an acid or a base or a group which is deprotected by heat, and the following general formula (1):

In the formula, Z is a hydrogen atom or a methyl group. Also, the bond at both ends represents a single bond to another part in the molecule. }
A negative photosensitive resin composition comprising an ether compound containing in the molecule one or more structural units represented by and a photopolymerization initiator (C).
[12]
12. The negative photosensitive resin composition according to item 11, wherein the (D) ether compound contains two or more structural units represented by the general formula (1) in a molecule.
[13]
13. The negative photosensitive resin composition according to item 11 or 12, wherein the one or more protected amino groups is an amino group protected by a tert-butoxycarbonyl group.
[14]
The (A) polyimide precursor is represented by the following general formula (2):

Wherein 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 hydrogen It is an atom or a monovalent organic group, and at least one of R ₁ and R ₂ is a monovalent organic group having a polymerizable group at its end. }
The negative photosensitive resin composition according to any one of items 11 to 13, comprising a polyimide precursor having a structural unit represented by
[15]
In the general formula (2), at least one of R ₁ and R ₂ has the following general formula (3):

Wherein L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. The negative photosensitive resin composition according to item 14, which is a monovalent organic group represented by
[16]
The (A) polyimide precursor is represented by the following general formula (4):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
The negative photosensitive resin composition as described in 14 or 15 containing the polyimide precursor which has a structural unit represented by these.
[17]
The (A) polyimide precursor is represented by the following general formula (5):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
The negative photosensitive resin composition as described in 14 or 15 containing the polyimide precursor which has a structural unit represented by these.
[18]
The (A) polyimide precursor is represented by the following general formula (6):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
The negative photosensitive resin composition as described in 14 or 15 containing the polyimide precursor which has a structural unit represented by these.
[19]
The (A) polyimide precursor is represented by the following general formula (4):

{Wherein R ₁ , R ₂ and n ₁ are as defined in the above general formula (2), provided that R ₁ , R ₂ and n ₁ in the general formula (5) are 4) R ₁ , R ₂ and n _{1 in} 4) are independently selected. }
The negative photosensitive resin composition as described in 14 or 15 which contains both of the polyimide precursor which has a structural unit represented by these.
[20]
The (A) polyimide precursor is represented by the following general formula (4):

{Wherein R ₁ , R ₂ and n ₁ are as defined in the above general formula (2), provided that R ₁ , R ₂ and n ₁ in the general formula (6) are 4) R ₁ , R ₂ and n _{1 in} 4) are independently selected. }
The negative photosensitive resin composition as described in 14 or 15 which contains both of the polyimide precursor which has a structural unit represented by these.
[21]
100 parts by mass of the above (A) polyimide precursor
0.1 to 30 parts by mass of the above (D) ether compound, based on 100 parts by mass of the above (A) polyimide precursor,
The negative photosensitive resin according to any one of items 11 to 20, comprising 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor Composition.
[22]
(A) polyimide precursor;
(E) One or more amino groups protected by an acid or a base or a thermally deprotected group, and a urethane compound containing at least one hydroxyl group in the molecule; and (C) a photopolymerization initiator , Negative photosensitive resin composition.
[23]
The (E) urethane compound has at least one tert-butoxycarbonyl group, benzyloxycarbonyl group or 9-fluorenylmethyloxycarbonyl (Fmoc) group bonded to an aliphatic chain or alicyclic amino group in the molecule. Item 22. The negative photosensitive resin composition according to Item 22.
[24]
24. The negative photosensitive resin according to item 22 or 23, wherein at least one of the nitrogen atoms of the protected one or more amino groups of the (E) urethane compound is at the γ or ε position of the hydroxyl group in the molecule. Resin composition.
[25]
The negative photosensitive resin composition according to any one of items 22 to 24, wherein the one or more protected amino groups is an amino group protected by a tert-butoxycarbonyl group.
[26]
The (A) polyimide precursor is represented by the following general formula (2):

Wherein 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 hydrogen It is an atom or a monovalent organic group, and at least one of R ₁ and R ₂ is a monovalent organic group having a polymerizable group at its end. }
The negative photosensitive resin composition according to any one of items 22 to 25, comprising a polyimide precursor having a structural unit represented by
[27]
In the general formula (2), at least one of R ₁ and R ₂ has the following general formula (3):

Wherein L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. The negative photosensitive resin composition according to item 26, which is a monovalent organic group represented by
[28]
The (A) polyimide precursor is represented by the following general formula (4):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
The negative photosensitive resin composition as described in 26 or 27 containing the polyimide precursor which has a structural unit represented by these.
[29]
The (A) polyimide precursor is represented by the following general formula (5):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
The negative photosensitive resin composition as described in 26 or 27 containing the polyimide precursor which has a structural unit represented by these.
[30]
The (A) polyimide precursor is represented by the following general formula (6):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the above general formula (2). }
The negative photosensitive resin composition as described in 26 or 27 containing the polyimide precursor which has a structural unit represented by these.
[31]
The (A) polyimide precursor is represented by the following general formula (4):

{Wherein R ₁ , R ₂ and n ₁ are as defined in the above general formula (2), provided that R ₁ , R ₂ and n ₁ in the general formula (5) are 4) R ₁ , R ₂ and n _{1 in} 4) are independently selected. }
The negative photosensitive resin composition as described in 26 or 27 containing both of the polyimide precursor which has a structural unit represented by these.
[32]
The (A) polyimide precursor is represented by the following general formula (4):

{Wherein R ₁ , R ₂ and n ₁ are as defined in the above general formula (2), provided that R ₁ , R ₂ and n ₁ in the general formula (6) are 4) R ₁ , R ₂ and n _{1 in} 4) are independently selected. }
The negative photosensitive resin composition as described in 26 or 27 containing both of the polyimide precursor which has a structural unit represented by these.
[33]
The (E) urethane compound is Nα- (tert-butoxycarbonyl) -L-triptophanol, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, or the following chemical formula (1):

The photosensitive resin composition according to any one of items 22 to 32, which is a urethane compound represented by
[34]
100 parts by mass of the above (A) polyimide precursor
0.1 to 30 parts by mass of the (E) urethane compound, based on 100 parts by mass of the (A) polyimide precursor,
The negative photosensitive resin according to any one of items 22 to 33, comprising 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor Composition.
[35]
34. A method for producing a polyimide, which cures the negative photosensitive resin composition according to any one of items 1 to 34.
[36]
(1) applying the negative photosensitive resin composition according to any one of items 1 to 34 on a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the steps of: heat-treating the relief pattern to form a cured relief pattern.

According to the present invention, a high-resolution is obtained, and a negative photosensitive resin composition that suppresses the generation of voids at the interface of the Cu layer in contact with the resin layer after a high temperature storage test, and a method for producing the same. Can be provided. It is possible to provide a method for forming a cured relief pattern using the negative photosensitive resin composition. In one embodiment, a negative photosensitive resin composition having high chemical resistance, high resolution, and high void suppression effect, a method for producing the same, and a cured relief pattern using the negative photosensitive resin composition A method of formation can be provided.

Hereinafter, modes for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.
Throughout the specification, the structures represented by the same symbol in the general formula may be identical to or different from each other when a plurality of structures are present in the molecule.

<Negative photosensitive resin composition>
The negative photosensitive resin composition according to the first embodiment is
(A) polyimide precursor;
(B) A plurality of amino groups protected by an acid or a base or a group to be deprotected by heat, having a molecular weight of 250 to 600, and the plurality of protected amino groups having an aliphatic chain or alicyclic structure A base-protected compound which is an amino group of the formula and has a solubility parameter value of 20.0 or more and 24.0 or less; and (C) a photopolymerization initiator.
The negative photosensitive resin composition according to the second present embodiment is
(A) polyimide precursor;
(D) One or more amino groups protected by an acid or a base or a group which is deprotected by heat, and the following general formula (1):

In the formula, Z is a hydrogen atom or a methyl group. Also, the bond at both ends represents a single bond to another part in the molecule. }
And an ether compound containing in the molecule thereof one or more structural units represented by: and (C) a photopolymerization initiator.
The negative photosensitive resin composition according to the third embodiment is:
(A) polyimide precursor;
(E) One or more amino groups protected by an acid or a base or a thermally deprotected group, and a urethane compound containing at least one hydroxyl group in the molecule; and (C) a photopolymerization initiator .

(A) Polyimide Precursor (A) The polyimide precursor in the first to third embodiments is a resin component contained in a negative photosensitive resin composition, and is converted to a polyimide by heat cyclization treatment. Be done.
The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (2).

Wherein 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 hydrogen It is an atom or a monovalent organic group. }

At least one of R ₁ and R ₂ has the following general formula (3):

Wherein L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. It is a monovalent organic group represented by}.

Although n ₁ in the general formula (2) is not limited as long as it is an integer of 2 to 150, it is preferably an integer of 3 to 100, and more preferably 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition. The integer of is more preferable.
In the general formula (2), the tetravalent organic group represented by X ₁ is preferably an organic group having a carbon number of 6 to 40, more preferably, in terms of achieving both heat resistance and photosensitivity. An —COOR ₁ group and an —COOR ₂ group and an —CONH— group are an aromatic group or an alicyclic aliphatic group in which each other is in the ortho position. Specific examples of the tetravalent organic group represented by X ₁ include an aromatic ring-containing organic group having 6 to 40 carbon atoms, for example, the following general formula (20):

Wherein R 6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group, and l is 0 Is an integer selected from -2, m is an integer selected from 0-3, and n is an integer selected from 0-4. }
Although the group which has a structure represented by these is mentioned, It is not limited to these. The structure of X ₁ may be one kind or a combination of two or more kinds. The X ₁ group having the structure represented by the above formula (20) is particularly preferable in that both the heat resistance and the photosensitive characteristics are compatible.

In the general formula (2), the divalent organic group represented by Y ₁ is preferably an aromatic group having a carbon number of 6 to 40, in terms of achieving both heat resistance and photosensitivity, and, for example, Following formula (21):

Wherein R 6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group, and n is It is an integer selected from 0-4. }
Although the structure represented by these is mentioned, it is not limited to these. The structure of Y ₁ may be one kind or a combination of two or more kinds. The Y ₁ group having the structure represented by the above formula (21) is particularly preferable in that both the heat resistance and the photosensitive characteristics are compatible.

L ₁ in the above general formula (3) is preferably a hydrogen atom or a methyl group, and L ₂ and L ₃ are preferably hydrogen atoms from the viewpoint of photosensitive properties. Also, m ₁ is 2 or more integer of 10 or less from the viewpoint of photosensitive properties, preferably 2 to 4 integer.

In one embodiment, the (A) polyimide precursor has the following general formula (4):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the general formula (2). }
It is preferable that it is a polyimide precursor which has a structural unit represented by these.
In the general formula (4), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (3). When the (A) polyimide precursor contains the polyimide precursor represented by the general formula (4), the resolution effect is particularly enhanced.

In one embodiment, the (A) polyimide precursor has the following general formula (5):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the general formula (2). }
It is preferable that it is a polyimide precursor which has a structural unit represented by these.
In the general formula (5), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (3). The effect of resolution is particularly high by including the polyimide precursor represented by the general formula (5) in addition to the polyimide precursor represented by the general formula (4) (A) Become. In that case, the general formula (5) _{_R} 1, _R ₂ in, and _{n 1} is the general formula (4) _{_R} 1, _R ₂ in, and the _{n 1} are independently selected.

In one embodiment, the (A) polyimide precursor has the following general formula (6):

In the formula, R ₁ , R ₂ and n ₁ are as defined in the general formula (2). }
It is preferable that it is a polyimide precursor which has a structural unit represented by these.
In the general formula (6), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (3). The effect of resolution is particularly high when the polyimide precursor (A) includes the polyimide precursor represented by the general formula (6) in addition to the polyimide precursor represented by the general formula (4) Become. In that case, the general formula (6) _{_R} 1, _R ₂ in, and _{n 1} is the general formula (4) _{_R} 1, _R ₂ in, and the _{n 1} are independently selected.

(A) Preparation Method of Polyimide Precursor (A) The polyimide precursor is prepared by _first using the tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X ₁ and an alcohol having a photopolymerizable unsaturated double bond. And optionally after reaction with an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and It is obtained by carrying out the amide polycondensation of diamines containing a divalent organic group Y ₁ .

(Preparation of acid / ester)
The tetracarboxylic acid dianhydride containing a tetravalent organic group X ₁ suitably used to prepare the (A) polyimide precursor in this embodiment is a tetracarboxylic acid represented by the above general formula (20). Acid dianhydrides, for example, pyromellitic anhydride, diphenylether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride , Biphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride, diphenyl sulfone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3 ', 4, 4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3 , 3-hexafluoropropane etc., preferably Water pyromellitic acid, diphenyl ether-3,3 ', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3 ', Mention may be made, without limitation, of 4,4′-tetracarboxylic acid dianhydride. In addition, it is possible to use two or more of them in combination as a matter of course that they can be used alone.

Examples of alcohols having a photopolymerizable unsaturated double bond, which are suitably used to prepare the (A) polyimide precursor in this embodiment, include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy. 3-Propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl acrylate Cole, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, Examples thereof include 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

Examples of the above-mentioned alcohols having a photopolymerizable unsaturated double bond include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-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 monomethyl ether It is also possible to partially mix and use alcohols having no unsaturated double bond such as ether, tetraethylene glycol monoethyl ether and benzyl alcohol.

Moreover, you may mix and use the non-photosensitive polyimide precursor prepared only with the said alcohol which does not have the said unsaturated double bond as a polyimide precursor with a photosensitive polyimide precursor. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

The above suitable tetracarboxylic acid dianhydride and the above alcohol are dissolved by stirring and mixing in the presence of a basic catalyst such as pyridine in a solvent as described later at a temperature of 20 to 50 ° C. for 4 to 10 hours As a result, the esterification reaction of the acid anhydride proceeds to obtain the desired acid / ester.

(Preparation of Polyimide Precursor)
In the above acid / ester form (typically, a solution in a solvent described below), under ice-cooling, a suitable dehydrating condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1 -Carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate etc. are added and mixed to make the acid / ester body a polyanhydride, Further, a solution obtained by separately dissolving or dispersing a diamine containing a divalent organic group Y ₁ suitably used in the present embodiment in a solvent is added dropwise to obtain an intended polyimide precursor by amide polycondensation. Can. Alternatively, the acid / ester body is acid-chloridized with thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain a target polyimide precursor. be able to.

Examples of diamines containing a divalent organic group Y ₁ suitably used in the present embodiment include diamines having a structure represented by the above general formula (21), for example, p-phenylenediamine, m-phenylenediamine, 4,4-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl 4,4'-Diaminobenzophenone, 3,4'-diaminobenzophene , 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) ) Phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyne) ) Benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine Sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen and the like For example 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-Dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro Examples include, but are not limited to, -4,4'-diaminobiphenyl and mixtures thereof.

After completion of the amide polycondensation reaction, the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution is separated by filtration if necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is The polymer component is charged into the obtained polymer component, and the polymer component is precipitated, and further, the polymer is purified by repeating the re-dissolution, re-precipitation operation and the like, and vacuum drying is performed to obtain the desired polyimide precursor. Let go. In order to improve the degree of purification, the solution of the polymer may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

The molecular weight of the (A) polyimide precursor is preferably 8,000 to 150,000, and 9,000 to 50,000, as measured by gel permeation chromatography as a polystyrene equivalent weight average molecular weight. Is more preferred. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodispersed polystyrene. As standard monodispersed polystyrene, it is recommended to select from Showa Denko organic solvent-based standard sample STANDARD SM-105.

(B) Base-Protected Compound The (B) base-protected compound in the first embodiment has a plurality of amino groups protected by an acid or a base or a group which is deprotected by heat, and has a molecular weight of 250 to 600. The protected amino group is an aliphatic linear or alicyclic amino group, and the solubility parameter has a value of 20.0 to 22.0.

The molecular weight of the (B) base-protected compound is 250 to 600. If the molecular weight is 250 or more, the base protection compound remains in the film even after thermosetting, and the Cu void suppressing effect can be exhibited. The molecular weight is preferably 300 or more, and more preferably 340 or more. On the other hand, from the viewpoint of obtaining high resolution, the molecular weight is preferably 600 or less, more preferably 550 or less, more preferably 450 or less, and more preferably 400 or less.

(B) The plurality of protected amino groups of the base protection compound is an aliphatic chain or alicyclic amino group. Aliphatic chain-like and alicyclic amino groups have high nucleophilicity as compared to aromatic amino groups, so that the introduction of protecting groups is easy.

(B) The value of the solubility parameter of the base protected compound is 20.0 to 24.0. As used herein, "solubility parameter" is the solubility parameter determined by the Hoy calculation method. If the solubility parameter is 20.0 or more, the solubility in the solvent is sufficiently high, preferably 20.5 or more, more preferably 21.0 or more. When the solubility parameter is 24.0 or less, the affinity to the solvent becomes appropriate, and the chemical solution hardly penetrates into the cured relief pattern during the chemical resistance test, and a cured relief pattern excellent in chemical resistance can be obtained. From the viewpoint of chemical resistance, the value of the solubility parameter is preferably 23.5 or less, more preferably 23.0 or less, still more preferably 22.5 or less, still more preferably 22.0 or less.

Preferable examples of the acid or base or the thermally deprotected group include tert-butoxycarbonyl group and Fmoc group, but the present invention is not limited thereto. Here, the Fmoc group refers to a 9-fluorenylmethyloxycarbonyl group. More preferably, the one or more amino groups are amino groups protected with a tert-butoxycarbonyl group.

When the amino group is deprotected during heat curing, a thermally deprotected group is preferred because the basicity of the amino group promotes imidization. In addition, from the viewpoint of the easiness of synthesis of the compound and the viewpoint of resolution, the compound is preferably a compound protected with a tert-butoxycarbonyl group. The compound protected with the tert-butoxycarbonyl group is considered to exhibit good resolution because the solubility in a developer is good and the residue is suppressed.

When the above base protection compound is used, good chemical resistance and resolution, and a Cu void suppression effect can be obtained. Without being bound by theory, the reason why good chemical resistance can be obtained is that the flowability of the polyimide resin in the heat curing process is improved by including a compound having a certain range of solubility parameter and molecular weight. It is considered to be. As a result, it is considered that the improvement of the fluidity promotes the stacking of the imide rings and suppresses the penetration of the chemical solution. Also, although the reason why good resolution can be obtained is unknown, it is considered that the base-protected compound is easily dissolved in the developer by having a certain range of solubility parameters, and the residue is suppressed. Be In addition, although the reason for showing the Cu void suppressing effect is not clear, having a plurality of nitrogen atoms derived from the protected amino group in the molecule makes it possible to interact strongly with the Cu ion, thereby diffusing the Cu. It is thought that it suppresses and, as a result, suppresses Cu void.

The number of protected amino groups contained in the molecule of the base protected compound is not limited as long as it is 2 or more. From the viewpoint of solubility in a solvent, the compound is preferably a compound in which the amino group of an amine selected from the group consisting of diamine, triamine and tetraamine is protected. From the viewpoint of coordination to copper, it is more preferable that the compound is a compound in which the amino group of diamine is protected. The base-protected compound preferably has at least one protected amino group at each end of the molecule. More preferably, the number of protected amino groups is two and the base protected compound preferably has one protected amino group at each end of the molecule.

It is preferable that the said base protection compound does not contain acidic groups, such as a carboxyl group, a sulfo group, and a phosphoric acid group. By not including these acidic groups, damage to the copper wiring is reduced. Moreover, it is preferable that the said base protection compound does not contain an alicyclic structure from a soluble viewpoint, and it is preferable that an aromatic group is not included from a chemical-resistant viewpoint. Similarly, from the viewpoint of chemical resistance, it is preferable not to contain a hydroxyl group.

Specific examples of the above base-protected compounds include, but are not limited to, 1,3-di-4-piperidylpropane, 1,4-butanediol (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, for example. 1,2-bis (2-aminoethoxy) ethane, 2,2-oxybis (ethylamine), 1,3-diaminopropane, m-xylylenediamine, p-xylylenediamine, 1,4-dicyclohexanediamine, Compounds in which an amino group is protected with a tert-butoxycarbonyl group, such as 1,4-bis (aminomethyl) cyclohexane and 1,3-bis (aminomethyl) cyclohexane, can be mentioned.

The amount of the base protection compound is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. (A) The content of the base protection compound is 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide precursor, thereby improving the Cu void suppression effect, the resolution improvement, and the chemical resistance improvement. A particularly excellent negative photosensitive resin composition can be obtained.

(C) Photopolymerization Initiator The (C) photopolymerization initiator used in the first to third embodiments will be described. As the photopolymerization initiator, a photoradical polymerization initiator is preferable, and benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyl diphenyl ketone, benzophenone derivatives such as dibenzyl ketone and fluorenone, 2, Acetophenone derivatives such as 2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc., thioxanthone derivatives such as thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, diethyl thioxanthone, benzyl, Benzyl derivatives such as benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione 2- (o-Methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione- Oximes such as 2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoylperchloride, aromatic biimidazoles, titanocenes, α- (n-octane Photoacid generators such as sulfonyloxyimino) -4-methoxybenzyl cyanide are preferably mentioned. That, without being limited thereto. Among the above-mentioned photopolymerization initiators, oximes are more preferable particularly in light of photosensitivity.

The compounding amount of the photopolymerization initiator (C) is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 1 part by mass to 8 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. It is. The said compounding quantity is 0.1 mass part or more from a photosensitivity or a viewpoint of patterning property, and is 20 mass parts or less from a viewpoint of the physical property of the photosensitive resin layer after hardening of a negative photosensitive resin composition.

The negative photosensitive resin composition of the present embodiment may further contain components other than the components (A) to (C). The components other than the components (A) to (C) include, but are not limited to, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion assistants, sensitizers, photopolymerizable unsaturated monomers, Thermal polymerization inhibitors and the like can be mentioned.

(D) Ether Compound In the second embodiment, the (D) ether compound is an acid or a base or an amino group protected by a group which is deprotected by heat, and a compound represented by the following general formula (1):

In the formula, Z is a hydrogen atom or a methyl group. Also, the bond at both ends represents a single bond to another part in the molecule. It is an ether compound which contains in a molecule the structural unit represented by}.
The ether compound may have at least one structural unit represented by the above general formula (1) at any position in the molecule, and the arrangement of the structural unit in the molecule is not limited. For example, the ether compound may have a plurality of the structural units in succession in the molecule, and another structure may be interposed between the structural units. The structural units may be regularly arranged in the molecule of the ether compound, or may be randomly arranged.

As an ether compound, for example, 1,4-butanol bis (3-aminopropyl) ether, 1,2-bis (2-aminoethoxy) ethane, 2,2′-oxybis (ethylamine), 1,14-diamino- 3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis (3-aminopropyl) ether, or 1,11-diamino-3,6,9-trioxaundecane The amino group may be a compound protected by an acid or base or a group which is deprotected by heat. As commercially available ether compounds, JEFFAMINE (registered trademark) D-230, D-400, D-2000, D-4000, M-600, M-1000, M-2005, M-2070, T-403, T- The amino group of 3000, T-5000, HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, XTJ-435, or XTJ-436 is removed with acid or base or heat. Protecting groups include, but are not limited to, protected compounds.

When the above ether compound is used, good chemical resistance and resolution, and a Cu void suppression effect can be obtained. Without being bound by theory, it is believed that the reason why good chemical resistance can be obtained is that the fluidity of the polyimide resin in the heat curing process is improved by including a compound having a flexible ether bond. Be As a result, it is considered that the improvement of the fluidity promotes the stacking of the imide rings and suppresses the penetration of the chemical solution. Although the reason why good resolution can be obtained is unknown, it is considered that the structural portion of the general formula (1) is easily dissolved in the developer and the residue is suppressed. In addition, the reason for showing the Cu void suppression effect is not clear, but it is possible to contain the nitrogen atom derived from the protected amino group and the ether group derived from the structure of the above general formula (1) in the same molecule The interaction with Cu ions becomes strong, which suppresses the diffusion of Cu and, as a result, the Cu void is considered to be suppressed.

The number of protected amino groups contained in the molecule of the ether compound is not limited, but from the viewpoint of solubility in a solvent, amino of an amine selected from the group consisting of monoamines, diamines, triamines, and tetraamines. It is preferably a compound in which a group is protected, and more preferably a compound in which an amino group of a monoamine or diamine is protected. On the other hand, from the viewpoint of coordination to copper, it is particularly preferable that the compound is a compound in which the amino group of diamine is protected. When the number of protected amino groups is two or more, the ether compound has at least one protected amino group at each end of the molecule containing the structural unit represented by the above general formula (1) Is preferred. More preferably, the number of protected amino groups is two, and the ether compound has one protected amino group at each end of the molecule containing the structural unit represented by the above general formula (1). Is preferred.

Moreover, it is preferable that the structural unit of the said General formula (1) contained in the molecule | numerator of the said ether compound is two or more. By including two or more structural units of the general formula (1), the resolution is further improved. On the other hand, if the number of structural units of the general formula (1) is too large, swelling occurs in the pattern development step and the resolution deteriorates, so the structure of the general formula (1) contained in the molecule The number of units is preferably 100 or less, more preferably 50 or less, and particularly preferably 30 or less.

When two or more structural units of the general formula (1) are contained, Z in the general formula (1) may be identical or different, but is preferably identical. Further, Z in the general formula (1) is preferably a hydrogen atom from the viewpoint of the Cu void suppressing effect. It is considered that steric hindrance is reduced and coordination to Cu is improved by the fact that the vicinity of the ether group is a hydrogen atom.

The ratio (molar ratio) of the total number of protected amino groups contained in the molecule of the ether compound to the total number of structural units of the general formula (1) is 2: 1 to 2:16. The ratio is preferably 2: 1 to 2: 8, and more preferably 2: 2 to 2: 6. By being in this range, the effect of suppressing Cu voids is enhanced.

It is preferable that the said ether compound does not contain acidic groups, such as a carboxyl group, a sulfo group, and a phosphoric acid group. By not including these acidic groups, damage to the copper wiring is reduced. The ether compound preferably does not contain an alicyclic structure from the viewpoint of solubility, and preferably does not contain an aromatic group from the viewpoint of chemical resistance. Similarly, from the viewpoint of chemical resistance, it is preferable not to contain a hydroxyl group.

As a specific example of the said ether compound, although it is not limited, for example, The ether compound represented by the following chemical formula is preferable.

Depending on the type of the ether compound, it is considered that the protective group of the amino group may be decomposed in the heat curing process, but it may or may not be decomposed.

The amount of the ether compound is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. (A) By blending in the range of 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide precursor, especially the effects of Cu void suppression effect, resolution improvement and chemical resistance improvement An excellent negative photosensitive resin composition can be obtained.

(E) Urethane Compound In the third embodiment, the (E) urethane compound has one or more amino groups protected by an acid or a base or a group which is deprotected by heat, and a hydroxyl group in the molecule. Including one.

The number of protected amino groups contained in the molecule of the urethane compound is not limited, but from the viewpoint of solubility in a solvent, preferably an amine selected from the group consisting of monoamines, diamines, triamines, and tetraamines. The compound is preferably a compound in which the amino group is protected, more preferably a compound in which the amino group of monoamine or diamine is protected, still more preferably a compound in which the amino group of monoamine is protected.

(E) The urethane compound is preferably a tert-butoxycarbonyl group, a benzyloxycarbonyl group, or 9 bonded to an aliphatic amino group, more particularly to an aliphatic chain or alicyclic amino group. Aliphatic amino groups containing at least one fluorenylmethyloxycarbonyl (Fmoc) group in the molecule and at least one hydroxyl group in the molecule are linear primary or secondary amino groups, or It refers to an amino group in which an aromatic group or a heterocyclic group is not directly bonded to the nitrogen atom of the cyclic secondary amino group. That is, the urethane compound used in the present embodiment has the following general formula (XI):

Wherein R ₁₀ is either a tert-butoxycarbonyl group or a benzyloxycarbonyl group or an Fmoc group, and R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a hydroxyl group or a carbon number Either one of an organic group of 1 to 20 or an organic group of 1 to 20 carbon atoms having a hydroxyl group, and at least one of R ₁₁ , R ₁₂ and R ₁₃ is a carbon having a hydroxyl group or a hydroxyl group It is any of the organic groups of 1 to 20. }
Or the following general formula (XII):

Wherein R ₁₀ is either a tert-butoxycarbonyl group or a benzyloxycarbonyl group or an Fmoc group, and R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ are each independently The hydrogen atom, the hydroxyl group, the organic group having 1 to 20 carbon atoms, or the organic group having 1 to 20 carbon atoms having a hydroxyl group, at least one of R ₁₁ , R ₁₂ and R ₁₃ is It is any of a C 1-20 organic group having a hydroxyl group or a hydroxyl group. }
Can be represented by The organic group having 1 to 20 carbon atoms includes a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aromatic group and the like. These organic groups may contain, in the organic group, a bond or a substituent containing a nitrogen atom other than a hydrocarbon group, an oxygen atom, a sulfur atom or the like, and these have a cyclic structure whether linear or branched. May be included.

In the above formulas (XI) or (XII), R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a hydroxyl group, an organic group having 1 to 20 carbon atoms, Or any of C 1-20 organic groups having a hydroxyl group, provided that at least one of R ₁₁ , R ₁₂ and R ₁₃ is a hydroxyl group or an organic group having 1 to 20 carbon atoms having a hydroxyl group It is either. In addition, any two of R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ may be combined to form a cyclic structure, and even if it has a hydroxyl group in this cyclic structure Good.

The bond or substituent other than the hydrocarbon group in the organic group of R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ is not particularly limited as long as the effects of the present invention are not impaired. Ether bond, carbonyl bond, amide bond, urethane bond, urea bond, thiourea bond, azo bond, ester bond, urethane bond, hydroxyl group, amino group, aldehyde group, sulfo group, nitro group, azo group, imino group, nitroso group And diazo groups, ethoxy groups, methoxy groups, cyano groups, heterocyclic groups and the like, and from the viewpoint of stability, heterocyclic groups or hydroxyl groups are preferable.

When the above-mentioned urethane compound is used, good resolution and Cu void suppression effect can be obtained. The resolution is improved because the photosensitive resin composition contains the compound having the above structure, so that the solubility of the resin composition in the developer becomes good, and the residue is suppressed. it is conceivable that. In addition, it is speculated that the above-mentioned structure improves the interaction with Cu, prevents the diffusion of Cu ions, and suppresses Cu voids.

Examples of the above urethane compound include the following general formula (XIII):

[Wherein, R ₁₀ is either a tert-butoxycarbonyl group, a benzyloxycarbonyl group or an Fmoc group. )
The compounds represented by the above can be mentioned, but not limited thereto.

The (E) urethane compound is preferably a urethane compound which does not have any of the acidic groups contained in the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group. When the urethane compound does not have an acidic group, the effect of suppressing Cu voids in particular is enhanced.

The (E) urethane compound is preferably a urethane compound in which at least one nitrogen atom to which a tert-butoxycarbonyl group, a benzyloxycarbonyl group or an Fmoc group is bonded is at the γ- or ε-position of the hydroxyl group in the molecule. By the fact that the hydroxyl group in the molecule is at the γ position or the ε position with respect to the nitrogen atom, a particularly good Cu void suppression effect can be obtained. Although the reason is not clear, it is thought that the hydroxyl group at a suitable position with respect to the nitrogen atom interacts more strongly with the Cu ion, thereby suppressing the diffusion of Cu and consequently suppressing the Cu void. Be

The (E) urethane compound is more preferably a urethane compound containing at least one tert-butoxycarbonyl group bonded to an aliphatic chain or alicyclic amino group in the molecule. Although the reason is unknown, it is considered that the inclusion of the tert-butoxycarbonyl group in the molecule makes the solubility of the unexposed area in the developer even better and the resolution becomes better. For example, compounds in which R ₁₀ in the above formula (XIII) is a tert-butoxycarbonyl group can be mentioned.

(E) The urethane compound is Nα- (tert-butoxycarbonyl) -L-triptophanol, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, or the following chemical formula (1):

It is more preferable that it is a urethane compound represented by these. In the case of the above compounds, the effects of both the resolution and the Cu void suppression effect are particularly excellent.

Depending on the type of urethane compound, it is thought that the tert-butoxycarbonyl group, benzyloxycarbonyl group or Fmoc group bonded to the aliphatic amino group may be decomposed in the heat curing process, but it may or may not be decomposed. May be

The compounding amount of the (E) urethane compound is preferably 0.01 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (A) resin. The amount is preferably 0.01 parts by mass or more from the viewpoint of Cu void suppression, and preferably 20 parts by mass or less from the viewpoint of resolution. (A) A photosensitive resin composition particularly excellent in both the Cu void suppressing effect and the resolution improvement effect by blending in a range of 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin You can get it.

The negative photosensitive resin compositions according to the first to third embodiments of the present invention comprise, in addition to the components (A) to (E) described above, a solvent, a nitrogen-containing heterocyclic compound, a hindered phenol compound, an organic titanium compound, It may also contain other components such as adhesion promoters, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors.

Solvents Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols and the like, and examples thereof include N-methyl-2 -Pyrrolidone, N, N-dimethylacetamide, N, 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, tetrahydrofurfuryl alcohol, ethylene Use glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. be able to. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl urea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoint of resin solubility, resin composition stability, and adhesion to a substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol and tetrahydrofurfuryl alcohol are preferred.

Among such solvents, those which completely dissolve the produced polymer are preferable, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethyl Urea, gamma butyrolactone and the like can be mentioned.

In the photosensitive resin composition of the present embodiment, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. More preferably, it is in the range of 125 to 500 parts by mass.

Nitrogen-Containing Heterocyclic Compound In the case of forming a cured film on a substrate made of copper or a copper alloy using the photosensitive resin composition of the present embodiment, a negative photosensitive resin is used to suppress discoloration on copper. The composition may optionally contain a nitrogen-containing heterocyclic compound. Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives.

As the azole compound, 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, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-, Bis (α, α-dimethyl bene Ndyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5 -Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H-tet Tetrazole, 1-methyl -1H- tetrazole, and the like.

Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methyl guanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Guanine, N- (3-ethylphenyl) guanine, 2-a Adenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, it includes 8-aza hypoxanthine or their derivatives.

When the photosensitive resin composition contains the azole compound or the purine derivative, the compounding amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and From the viewpoint, 0.5 to 5 parts by mass is more preferable. When the compounding quantity with respect to 100 mass parts of (A) polyimide precursors of an azole compound is 0.1 mass part or more, when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, copper or Discoloration of the copper alloy surface is suppressed, and when it is 20 parts by mass or less, the photosensitivity is excellent.

Hindered Phenolic Compound In order to suppress the discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenolic compound. As the hindered phenol compound, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4, 4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (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], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylene bis (3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) ), Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate) Late, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2, -Dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxyl) -2,6-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy) -2,6-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl)- 3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethylmethyl-3 -Hydroxy-2,6-dimethylbenzyl] -1,3,5-to Azine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine- 2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5- Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1, 3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)- 1,3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H) , 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H , 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H) , 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydride) Roxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione etc. may be mentioned, but it is not limited thereto. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) )-Trione etc. are particularly preferred.

The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and is 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. Is more preferred. When the compounding quantity with respect to 100 mass parts of (A) polyimide precursors of a hindered phenol compound is 0.1 mass part or more, for example, when the photosensitive resin composition of this invention is formed on copper or a copper alloy, Discoloration and corrosion of copper or copper alloy are prevented, and when it is 20 parts by mass or less, the photosensitivity is excellent.

Organic titanium compound The negative photosensitive resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Usable organic titanium compounds include those 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, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition and a good pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate), titanium diisopropoxide bis (2,4-pentanedionate) And titanium diisopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxy), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis {2, 2- (allyloxymethyl) Butoxide]] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis (η5-2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compounds: for example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecyl benzene sulfonate) isopropoxide and the like.
V) Titanium oxide compounds: for example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate and the like.
VII) Titanate coupling agent: for example, isopropyl tridodecyl benzene sulfonyl titanate and the like.

Among them, the organic titanium compound exhibits at least one kind of compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound, thereby exhibiting better chemical resistance. It is preferable from the viewpoint of that. In particular, titanium diisopropoxide bis (ethylacetoacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H) -Pyrrol-1-yl) phenyl) titanium is preferred.

The blending amount in the case of blending the organic titanium compound is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance develop, and when the amount is 10 parts by mass or less, the storage stability is excellent.

Adhesion assistant In order to improve the adhesion between the film formed using the negative photosensitive resin composition of the present embodiment and the substrate, the negative photosensitive resin composition may optionally contain an adhesion assistant. Good. As adhesion assistants, γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene-1, 4-bis (N- [3-triet Silylyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane And silane coupling agents such as 3- (trialkoxysilyl) propyl succinic acid, and aluminum-based adhesions such as aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate, etc. An auxiliary agent etc. are mentioned.

Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesion. When the photosensitive resin composition contains an adhesion assistant, the amount of the adhesion assistant is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

As a silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name Silaace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.): Trade name SIM 6475.0), 3-Mercaptopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd .: trade name LS 1375, Azmax Co., Ltd .: trade name SIM 6474.0), mercaptomethyltrimethoxysilane (produced by Azmax Co., Ltd .: commodity Name: SIM 647 3.5 C), mercaptomethyl methyl dimethoxysilane (made by Azmax Co., Ltd .: trade name: SIM 647 3.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropyl Ethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-Mercaptoethyldiethoxymethoxysilane, 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane , 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (Shin-Etsu Chemical Co., Ltd. product name: LS 3610, Azmax Corporation product name: SIU 9055. 0), N- (3-trimethoxysilylpropyl) urea (made by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) Urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) Urea, N- (3- methoxy di Propoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxysilyl) Ethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilyl Butyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmaxx Co., Ltd .: trade name SLA 0598. 0), m-aminophenyltrimethoxysilane (asma S Co., Ltd .: trade name SLA 0599.0), p-aminophenyltrimethoxysilane (produced by Azmax Co., Ltd .: trade name SLA 0599. 1) aminophenyltrimethoxysilane (produced by Azmax Co., Ltd .: trade name SLA 0599.2), 2 -(Trimethoxysilylethyl) pyridine (manufactured by Azmaxx Co., Ltd .: trade name SIT 8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) Pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, Tra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxy) Silanes), 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] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxide Cyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilane Diol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-Butylmethylphenylsilanol, ethyl n-propylphenyl N, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol, isobutyl ethyl phenyl silanol, tert- butyl ethyl phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol, n- propyl diphenyl silanol, isopropyl diphenyl silanol, n- butyl diphenyl silanol, Examples include, but are not limited to, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol and the like. These may be used alone or in combination of two or more.

Among the above-mentioned silane coupling agents, as a silane coupling agent, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxy Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula:

The silane coupling agent which has a structure represented by these is preferable.

The blending amount in the case of using a silane coupling agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

Sensitizer The negative photosensitive resin composition of the present embodiment may optionally contain a sensitizer in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, 2,6-bis (4′-diethylaminobenzal) ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnana Myrylene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4'-dimethyl) Aminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7 -Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N- Phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-fu Nyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,1 2-d) Thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combinations of, for example, 2 to 5 types.

When the photosensitive resin composition contains a sensitizer for improving the photosensitivity, the compounding amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

Photopolymerizable Unsaturated Monomer The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth) acrylic compound which undergoes a radical polymerization reaction by a photopolymerization initiator is preferable, and although not particularly limited thereto, ethylene glycol or polyethylene such as diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc. Mono- or di-acrylates and methacrylates of glycols, Mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylates and dimethacrylates, diacrylates of 1,4-butanediol Dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate of neopentyl glycol And dimethacrylates, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or Mention may be made of compounds such as triacrylates and methacrylates, di-, tri- or tetra-acrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

When the photosensitive resin composition contains a monomer having the above-described photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the photopolymerizable unsaturated bond is ( A) The amount is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor.

Thermal Polymerization Inhibitor In order to improve the viscosity and the photosensitivity stability of the negative photosensitive resin composition at the time of storage in the state of a solution containing a solvent, in particular, the negative photosensitive resin composition of the present embodiment, A thermal polymerization inhibitor may optionally be included. As a thermal polymerization inhibitor, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-) Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

<Method of Manufacturing Hardened Relief Pattern and Semiconductor Device>
In this embodiment, (1) a step of applying the negative photosensitive resin composition of the above-described embodiment onto a substrate to form a resin layer on the substrate, and (2) exposing the resin layer A cured relief pattern comprising the steps of: (3) developing the resin layer after exposure to form a relief pattern; and (4) heating the relief pattern to form a cured relief pattern. Provide a manufacturing method of

(1) Resin layer formation process At this process, the negative photosensitive resin composition of this embodiment is apply | coated on a base material, and it is made to dry after that as needed, and a resin layer is formed. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating by a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., spray coating by a spray coater A method etc. can be used.

If necessary, the coating film containing the photosensitive resin composition can be dried. As a drying method, methods such as air drying, heat drying with an oven or a hot plate, vacuum drying and the like are used. Specifically, when air drying or heat drying is performed, drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the photosensitive resin layer can be formed on the substrate.

(2) Exposure Step In this step, the resin layer formed above is exposed to an ultraviolet light source or the like directly through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, mirror projection, stepper or the like. Expose.

Thereafter, post exposure bake (PEB) and / or post development bake may be performed according to any combination of temperature and time, as necessary, for the purpose of improving photosensitivity and the like. The range of baking conditions is that the temperature is 40 ° C. to 120 ° C., and the time is preferably 10 seconds to 240 seconds, but unless the various properties of the photosensitive resin composition of this embodiment are inhibited, It is not limited to this range.

(3) Relief pattern formation process At this process, an unexposed part is developed and removed among photosensitive resin layers after exposure. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of known methods for developing a photoresist, for example, a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment and the like can be used. You can use it by selecting the method. In addition, after development, post-development baking may be performed at any temperature and time combination, as necessary, for the purpose of adjusting the shape of the relief pattern and the like.

As a developing solution to be used for development, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and the poor solvent is preferable. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. . As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more types of each solvent, for example, several types may be used in combination.

(4) Curing Relief Pattern Forming Step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) a curing relief consisting of polyimide by imidizing the polyimide precursor. Convert to a pattern. As the heat curing method, various methods can be selected, such as using a hot plate, using an oven, using a temperature rising oven capable of setting a temperature program, and the like. The heating can be performed, for example, at 170 ° C. to 400 ° C. for 30 minutes to 5 hours. As the atmosphere gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present embodiment also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. Therefore, a semiconductor device can be provided which has a substrate which is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method of producing a cured relief pattern. The present invention can also be applied to a method of manufacturing a semiconductor device using a semiconductor element as a base material and including the method of manufacturing a cured relief pattern described above as part of the process. The semiconductor device of the present embodiment is a semiconductor having a surface protection film, an interlayer insulation film, an insulation film for rewiring, a protection film for a flip chip device, or a bump structure, which is formed by the above-mentioned method of manufacturing a hardening relief pattern. It can be formed as a protective film or the like of the device and combined with a known method of manufacturing a semiconductor device.

<Display device>
The present embodiment provides a display device comprising a display element and a cured film provided above the display element, wherein the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, as the cured film, there can be mentioned surface protective film of TFT liquid crystal display element and color filter element, insulating film, flattening film, projection for MVA type liquid crystal display device, and partition wall for organic EL element cathode. .

The negative photosensitive resin composition of the present embodiment is used in applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper clad plates, solder resist films, liquid crystal alignment films, etc. in addition to application to semiconductor devices as described above. It is also useful.

Hereinafter, the present embodiment will be specifically described by way of examples, but the present embodiment is not limited thereto. In Examples, Comparative Examples, and Production Examples, physical properties of the polymer or negative photosensitive resin composition were measured and evaluated according to the following methods.

<Measurement and evaluation method>
(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each resin was measured using a gel permeation chromatography method (in terms of standard polystyrene) under the following conditions.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M manufactured by Showa Denko 2 in series, or Shodex 805M / 806M series manufactured by Showa Denko Standard monodispersed polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko
Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP)
Flow rate: 1 mL / min.

(2) Preparation of a cured relief pattern on Cu 200 nm using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva) on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, a photosensitive resin composition prepared by the method described later is spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and prebaked on a hot plate at 110 ° C. for 180 seconds. Then, a coating film about 7 μm thick was formed. The coating film was irradiated with 500 mJ / cm 2 of energy by Prisma GHI (manufactured by Ultratech Co., Ltd.) using a mask with a test pattern. Next, this coating film is spray developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developer and 2.38% TMAH as a positive type. The relief pattern on Cu was obtained by rinsing with propylene glycol methyl ether acetate in the case of the negative type and with pure water in the case of the positive type.
Heat treating the wafer having the relief pattern formed on Cu at a temperature described in Table 1 for 2 hours in a nitrogen atmosphere using a programmed temperature curing furnace (VF-2000, manufactured by Koyo Lindberg) Thus, a cured relief pattern consisting of a resin about 4 to 5 μm thick was obtained on Cu.

(3) Evaluation of Resolution of Hardened Relief Pattern on Cu The hardened relief pattern obtained by the above method was observed under an optical microscope to determine the size of the minimum opening pattern. At this time, if the area of the opening of the obtained pattern is 1/2 or more of the corresponding pattern mask opening area, it is regarded as resolved, and the one having the smallest area among the resolved openings The length of the corresponding mask opening side was taken as the resolution. Those with a resolution of less than 10 μm were rated as “excellent”, those with 10 μm or more and less than 14 μm as “good”, those with 14 μm or more and less than 18 μm as “OK”, and those with 18 μm or more as “impossible”.

(4) High temperature storage test of cured relief pattern on Cu and subsequent evaluation of void area The wafer on which the cured relief pattern is formed on Cu is heated in a programmed curing oven (VF-2000 type, It heated at 150 degreeC in air for 168 hours using Koyo Lindberg Co., Ltd. product). Subsequently, using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.), the entire resin layer on Cu was removed by plasma etching. The plasma etching conditions are as follows.
Output: 133W
Gas type and flow rate: O2: 40 mL / min + CF 4: 1 mL / min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds The Cu surface from which the resin layer has been completely removed is observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (A Image Kun, manufactured by Asahi Kasei Corporation) The area of the void occupied on the surface of the Cu layer was calculated using When the total area of voids when the photosensitive resin composition described in Comparative Example 5 is evaluated is 100%, those having a total area ratio of voids of less than 50% are "excellent", not less than 50% and less than 75%. Those with "good" were judged as "good", those with 75% or more and less than 100% were judged as "OK" and those with 100% or more were judged as "impossible".

(5) Chemical resistance evaluation of cured relief pattern (polyimide coating film) The cured relief pattern formed on Cu was treated with a resist remover {a product made by ATMI, product name ST-44, main component is 2- (2-amino) It was immersed for 5 minutes in what heated (50 ° C.) ethanol, 1-cyclohexyl-2-pyrrolidone}, washed with running water for 1 minute, and air-dried. Thereafter, the film surface was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage due to the chemical solution such as a crack and the change rate of the film thickness after the chemical solution treatment. Evaluation criteria: No cracks or the like, and the film thickness change rate is “excellent” within 10% based on the film thickness before chemical immersion, “good” from 10 to 15%, “good”, 15 to 20% Those with "C" were evaluated as "OK", and those with cracks or those whose film thickness change rate exceeded 20% were classified as "Fail".

<(A) Production Example of Polyimide Precursor>
Production Example 1: (A) Synthesis of Polymer A-1 as Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) is placed in a 2 L separable flask, and 2-hydroxyethyl methacrylate ( 131.2 g of HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the reaction exotherm, the reaction mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone is added to the reaction mixture with stirring over 40 minutes, and subsequently, 4,4′-oxydianiline (ODA) A suspension of 93.0 g in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After stirring for 2 hours at room temperature, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 3 L of ethyl alcohol to form a precipitate consisting of a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer A-1). The molecular weight of the polymer (A-1) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 20,000.

Production Example 2 (A) Synthesis of Polymer A-2 as Polyimide Precursor In place of 155.1 g of 4,4′-oxydiphthalic acid dianhydride (ODPA) in Production Example 1, 3,3 ′, 4,4 A reaction was carried out in the same manner as in the above-mentioned Production Example 1 except that 147.1 g of '-biphenyltetracarboxylic acid dianhydride (BPDA) was used, to obtain a polymer (A-2). The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 22,000.

Production Example 3 (A) Synthesis of Polymer A-3 as Polyimide Precursor 50.2 g of p-phenylenediamine was used in place of 93.0 g of 4,4′-oxydianiline (ODA) in Production Example 1 The reaction was carried out in the same manner as described in Production Example 1 except for the above, to obtain a polymer (A-3). The molecular weight of the polymer (A-3) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 19,000.

Production Example 4: (A) Synthesis of Polymer A-4 as Polyimide Precursor (Polybenzoxazole Precursor)
In a 3 l separable flask, 183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), 63.3 g of pyridine It mixed and stirred at room temperature (25 degreeC), and was set as the uniform solution. To this, 118.0 g of 4,4'-diphenylether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was dropped from a dropping funnel. At this time, the separable flask was cooled by a water bath of 15 to 20.degree. The time required for the dropwise addition was 40 minutes, and the temperature of the reaction solution was 30 ° C. at maximum.
After 3 hours from the end of dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride is added to the reaction solution, and stirred at room temperature for 15 hours to allow 99% of all amine end groups of the polymer chain to be carboxy Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by monitoring the amount of remaining 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high speed stirring to disperse and precipitate the polymer, which was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC) method A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) was obtained.
The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL) and then treated with a cation exchange resin and an anion exchange resin, and the solution obtained thereby is ion-exchanged water The precipitated polymer was separated by filtration, washed with water and vacuum dried to obtain a purified polybenzoxazole precursor (polymer A-4).

<(B) Production Example of Base-Protected Compound>
Production Example 5 (B) Synthesis of Compound B-1 as a Base-Protected Compound Into a 1-L eggplant-shaped flask, 100 g of 1,3-di-4-piperidylpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol And stirred with a stirrer to make a homogeneous solution, and cooled to 5 ° C. or less with ice water. A solution of 228 g of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 200 g of ethanol was dropped to the solution by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-1. (Molecular weight: 411, solubility parameter: 20.2)

Preparation Example 6 (B) Synthesis of Compound B-2 as a Base-Protected Compound Into a 1-L eggplant-shaped flask, 100 g of 1,4-butanediol (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol was added, mixed and stirred by a stirrer to obtain a uniform solution, and cooled to 5 ° C. or less with ice water. A solution of 234 g of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 130 g of ethanol was dropped to the solution by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-2. (Molecular weight: 405, solubility parameter: 21.2)

Production Example 7 (B) Synthesis of Compound B-3 as a Base-Protected Compound In a 1-L eggplant-shaped flask, 100 g of diethylene glycol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol were added. The mixture was stirred with a stirrer to form a homogeneous solution, and cooled to 5 ° C. or less with ice water. To this, a solution of 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 120 g of ethanol was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-3. (Molecular weight: 421, solubility parameter: 21.5)

Production Example 8 (B) Synthesis of Compound B-4 as Base-Protected Compound Into a 1-L eggplant-shaped flask, 100 g of 1,2-bis (2-aminoethoxy) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 g of ethanol was added, mixed and stirred by a stirrer to obtain a uniform solution, and cooled to 5 ° C. or less with ice water. A solution of 319 g of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 150 g of ethanol was dropped into the solution by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-4. (Molecular weight: 348, solubility parameter: 21.9)

Production Example 9 (B) Synthesis of Compound B-5 as a Base-Protected Compound Into a 250-mL eggplant-shaped flask, 10 g of 2,2′-oxybis (ethylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of ethanol In addition, they were mixed and stirred by a stirrer to make a homogeneous solution, and cooled to 5 ° C. or less with ice water. To this, 46 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40 g of ethanol was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-5. (Molecular weight: 304, solubility parameter: 21.9)

Production Example 10: (B) Synthesis of Compound B-6 as a Base-Protected Compound In a 250-mL eggplant-shaped flask, 10 g of di-n-octylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of ethanol are added to obtain a stirrer. The mixture was mixed and stirred to form a homogeneous solution, and cooled to 5 ° C. or less with ice water. To this, 20 g of ethanol in which 20 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-6. (Molecular weight: 342, solubility parameter: 18.9)

Production Example 11 (B) Synthesis of Compound B-7 as a Base-Protected Compound Into a 250 mL eggplant-shaped flask, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Tokyo Chemical Industry Co., Ltd.) 10 g of ethanol and 10 g of ethanol were added, mixed and stirred by a stirrer to obtain a uniform solution, and cooled to 5 ° C. or less with ice water. To this, 12 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 12 g of ethanol was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction mixture was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound B-7. (Molecular weight: 611, solubility parameter: 22.0)

<(C) Photopolymerization initiator>
The (C) photopolymerization initiator used is shown below.
C-1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime C-2: Irgacure OXE01 (manufactured by BASF, trade name)

<(D) Production Example of Ether Compound>
Production Example 12 (D) Synthesis of Compound D-1 as an Ether Compound In a 1-L eggplant-shaped flask, 100 g of JEFFAMINE® M-600 (manufactured by Huntsman) and 100 g of ethanol are added and mixed and stirred with a stirrer The reaction solution was cooled to below 5 ° C. with ice water. A solution of 44 g of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 44 g of ethanol was dropped to the solution by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction mixture was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-1.

Production Example 13 (D) Synthesis of Compound D-2 as Ether Compound In a 1-L eggplant-type flask, 100 g of JEFFAMINE® M-1000 (manufactured by Huntsman) and 100 g of ethanol are added and mixed and stirred by a stirrer. The reaction solution was cooled to below 5 ° C. with ice water. To this, 26 g of ethanol in which 26 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction mixture was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-2.

Production Example 14 (D) Synthesis of Compound D-3 as an Ether Compound In a 1-L eggplant-type flask, 100 g of JEFFAMINE® D-400 (sold by Mitsui Chemicals Fine Inc.) and 100 g of ethanol were added. The mixture was stirred with a stirrer to form a homogeneous solution, and cooled to 5 ° C. or less with ice water. To this, 110 g of ethanol in which 110 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-3.

Production Example 15 (D) Synthesis of Compound D-4 as an Ether Compound In a 1-L eggplant type flask, 100 g of diethylene glycol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol The mixture was mixed and stirred by a stirrer to obtain a uniform solution, and cooled to 5 ° C. or less with ice water. To this, a solution of 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 120 g of ethanol was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-4.

Production Example 16 (D) Synthesis of Compound D-5 as an Ether Compound Into a 1-L eggplant-shaped flask, 100 g of 1,4-butanediol (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and ethanol 100 g was added, mixed and stirred by a stirrer to obtain a uniform solution, and cooled to 5 ° C. or less with ice water. A solution of 234 g of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 130 g of ethanol was dropped to the solution by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-5.

Production Example 17 (D) Synthesis of Compound D-6 as Ether Compound Into a 1-L eggplant-shaped flask, 100 g of 1,2-bis (2-aminoethoxy) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol And stirred with a stirrer to make a homogeneous solution, and cooled to 5 ° C. or less with ice water. A solution of 319 g of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 150 g of ethanol was dropped into the solution by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction mixture was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-6.

Production Example 18 (D) Synthesis of Compound D-7 as an Ether Compound In a 250 mL eggplant-type flask, 10 g of 2,2′-oxybis (ethylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of ethanol are added. The mixture was mixed and stirred by a stirrer to obtain a uniform solution, and cooled to 5 ° C. or less with ice water. To this, 46 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40 g of ethanol was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50 ° C. or less. Two hours after the completion of dropwise addition, the reaction mixture was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound D-7.

<(E) Urethane compound>
The (E) urethane compound used is shown below.
E-1: 1- (tert-butoxycarbonyl) -4-piperidinemethanol (made by Tokyo Chemical Industry Co., Ltd.)
E-2: 3- (carbobenzoxyamino) -1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-3: N-[(9H-fluoren-9-ylmethoxy) carbonyl] -D-serine (made by Tokyo Chemical Industry Co., Ltd.)
E-4: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-5: 40 g of 4-hydroxy-4-phenylpiperidine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 300 g of ethanol were added to a 3 L eggplant-shaped flask and mixed and stirred to obtain a uniform solution. To this, 54 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 g of ethanol was dropped by a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 60 ° C. or less. Two hours after the completion of dropwise addition, the reaction solution was evaporated under reduced pressure at 50 ° C. to obtain a urethane compound E-5 as a white solid (compound of the above-mentioned formula 1).
E-6: Nα- (tert-butoxycarbonyl) -L-triptophanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-7: N- (tert-butoxycarbonyl) -L-serine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-8: 1- (tert-butoxycarbonyl) -4-piperidine carboxylic acid (made by Tokyo Chemical Industry Co., Ltd.)
E-9: N- (tert-butoxycarbonyl) -4-hydroxyaniline (manufactured by Sigma Aldrich)
E-10: 2- (2-aminoethoxy) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.)

Example 1
A negative photosensitive resin composition was prepared by using the polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, 5 B of compound B-1 as a (B) base-protected compound, 1-phenyl-1,2-propanedione-2- (C) as a photopolymerization initiator 3 g of O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, corresponding to a photopolymerization initiator C-1): 3 g was dissolved in 150 g of γ-butyl lactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

Examples 2 to 15, Comparative Examples 1 and 2
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that it was prepared with the components and compounding ratios as shown in Tables 1 and 2, and was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, in the negative photosensitive resin composition of Example 1, the Cu surface was evaluated as "Poor" in void evaluation, resolution evaluation, and chemical resistance evaluation. The negative photosensitive resin compositions of Examples 2 to 15 were all "OK" or more in all of the Cu surface void evaluation, the resolution evaluation, and the chemical resistance evaluation. In particular, in Example 6 using polymers A-1 and A-2 as the polyimide precursor (A) and Example 7 using polymers A-1 and A-3, particularly excellent Cu surface void evaluation and The resolution evaluation was obtained. In addition, as the base-protected compound (B), when adding 5 parts by mass of B-2, B-3 or B-4 based on 100 parts by mass of the polymer, a particularly excellent void suppression effect on the Cu surface is obtained. It was done. On the other hand, in Comparative Example 1 using B-6 and Comparative Example 2 using B-7, the evaluation of resolution was “impossible”.

Example 16
A negative photosensitive resin composition was prepared by using the polymer A-1 by the following method, and the prepared composition was evaluated. (A) Polymer A-1 as a polyimide precursor: 100 g, (D) Compound D-1 as an ether compound: 5 g, (C) 1-phenyl-1,2-propanedione-2- (O) as a photopolymerization initiator 3 g of -ethoxycarbonyl) -oxime (hereinafter referred to as PDO, corresponding to photosensitizer C-1): was dissolved in 150 g of γ-butyl lactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 3.

Examples 17 to 31 and Comparative Examples 5 to 7
A negative photosensitive resin composition was prepared in the same manner as in Example 16 except that the components and the compounding ratio as shown in Table 1 were prepared, and evaluation was performed in the same manner as in Example 16. The results are shown in Tables 3 and 4.

Comparative Example 3
A positive photosensitive resin composition was prepared by using the polymer (A-4) by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer A-4, which is a polyoxazole precursor as a polymer, 5 g of D-4 as a compound, the following chemical formula (22) as a photosensitizer

In 100 g of GBL, 20 g of a photosensitive diazoquinone compound (corresponding to C-2, manufactured by Toyo Gosei Co., Ltd.) was obtained. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of GBL to obtain a positive photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 4.

Comparative Example 4
The same positive photosensitive resin composition as in Comparative Example 3 was prepared except that the ether compound was changed to D-4 and prepared using D-5, and evaluation was performed in the same manner as in Comparative Example 3. The results are shown in Table 4.

As is apparent from Tables 3 and 4, in the negative photosensitive resin composition of Example 16, the Cu surface void evaluation is “OK”, the resolution evaluation is “Good”, and the chemical resistance evaluation is “OK”. It became ". Similarly, the negative photosensitive resin compositions of Examples 17 to 31 were all "OK" or more in all of the Cu surface void evaluation, the resolution evaluation, and the chemical resistance evaluation. In particular, in Example 24 in which the polymers A-1 and A-2 were used as the (A) polyimide precursor, and in Example 25 in which the polymers A-1 and A-3 were used, particularly excellent resolution was obtained. It was done. In addition, when 5 parts by mass of D-4, D-5 or D-6 is added based on 100 parts by mass of the polymer as the (D) ether compound, a particularly excellent void suppression effect on the Cu surface is obtained. The On the other hand, in Comparative Example 5 using D-9 as the ether compound and Comparative Example 6 using D-10, the Cu surface void area was evaluated as “not good”. Further, in Comparative Examples 3 and 4 in which the polymer A-4 which is a polybenzoxazole precursor was used as the polymer, the Cu surface void area evaluation and the chemical resistance evaluation became “impossible”. And in the comparative example 7 which does not contain the (D) ether compound, it became "improper" by all evaluations.

Example 32
A negative photosensitive resin composition was prepared by using the polymer A-1 by the following method, and the prepared composition was evaluated. (A) Polymer A-1 as resin: 100 g, (E) Urethane compound 1- (tert-butoxycarbonyl) -4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd., (corresponding to E-4): 5 g, C) 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, corresponding to C-1): 4 g of a γ-butyl lactone (hereinafter referred to as a photosensitizer) In this case, the solution was dissolved in 150 g of GBL.The viscosity of the resulting solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The evaluation was made according to the method described above, and the results are shown in Table 5.

Examples 33 to 47, Comparative Examples 8 to 11
A negative photosensitive resin composition was prepared in the same manner as in Example 32 except that the components and the compounding ratio were as shown in Tables 5 and 6, and the evaluation was performed in the same manner as in Example 32. The results are shown in Tables 5 and 6.

As is clear from Tables 5 and 6, in the case of the photosensitive resin composition of Example 32, the evaluation of resolution was “good”, and the evaluation of void area on the Cu surface was “best”. Similarly, all of the photosensitive resin compositions of Examples 33 to 47 were “OK” or more in both of the resolution evaluation and the void area evaluation on the Cu surface. In particular, in Example 33 in which the polymers A-1 and A-2 were used as the resin (A) and Example 34 in which the polymers A-1 and A-3 were used, particularly excellent resolution was obtained. In addition, E-4, E-5, and E-6 are used as the (E) urethane compound, and when 5 parts by mass is added based on 100 parts by mass of the polymer, a particularly excellent void suppression effect on the Cu surface is obtained. It was seen. On the other hand, in Comparative Example 8 using E-8 as the urethane compound (E) and Comparative Example 8 using E-9, the resolution was "OK", but the void area of the Cu surface was evaluated as " It became impossible. Further, in Comparative Example 10 in which E-10 was used as the (E) urethane compound, although the evaluation of the void area on the Cu surface was “OK”, it became “Impossible” in the evaluation of resolution. And in the comparative example 11 which does not use the (E) urethane compound, it became "improper" by both resolution evaluation and void area evaluation of Cu surface.

By using the negative photosensitive resin composition according to the present embodiment, a cured relief pattern having high resolution can be obtained, and generation of voids on the Cu surface can be suppressed. The negative photosensitive resin composition of the present embodiment can be suitably used, for example, in the field of photosensitive materials useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

(A) polyimide precursor;
(B) It has a plurality of amino groups protected by an acid or a base or a group which is deprotected by heat, and has a molecular weight of 250 to 600, and the plurality of protected amino groups have an aliphatic chain or alicyclic A negative photosensitive resin composition comprising a base-protected compound which is an amino group of the formula and has a solubility parameter value of 20.0 to 24.0; and (C) a photopolymerization initiator.
The negative photosensitive resin composition according to claim 1, wherein the plurality of protected amino groups are amino groups protected with a tert-butoxycarbonyl group.
The (A) polyimide precursor has the following general formula (2):

Wherein 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 hydrogen It is an atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having a polymerizable group at its end. }
The negative photosensitive resin composition as described in any one of Claim 1 or 2 containing the polyimide precursor which has a structural unit represented by these.
In the general formula (2), at least one of R 1 and R 2 has the following general formula (3):

Wherein L 1 , L 2 and L 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer of 2 to 10. The negative photosensitive resin composition according to claim 3, which is a monovalent organic group represented by
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 3 or 4 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (5):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 3 or 4 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (6):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 3 or 4 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{Wherein R 1 , R 2 and n 1 are as defined in the general formula (2), provided that R 1 , R 2 and n 1 in the general formula (5) have the general formula ( 4) R 1 , R 2 and n 1 in 4) are independently selected. }
The negative photosensitive resin composition of Claim 3 or 4 which contains both of a polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
A polyimide precursor having a structural unit represented by the following general formula (6):

{Wherein R 1 , R 2 and n 1 are as defined in the general formula (2), provided that R 1 , R 2 and n 1 in the general formula (6) have the general formula ( 4) R 1 , R 2 and n 1 in 4) are independently selected. }
The negative photosensitive resin composition of Claim 3 or 4 which contains both of a polyimide precursor which has a structural unit represented by these.
100 parts by mass of the (A) polyimide precursor
0.1 to 30 parts by mass of the (B) base protecting compound, based on 100 parts by mass of the (A) polyimide precursor,
The negative photosensitive resin according to any one of claims 1 to 9, comprising 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor. Resin composition.
(A) polyimide precursor;
(D) One or more amino groups protected by an acid or a base or a group which is deprotected by heat, and the following general formula (1):

In the formula, Z is a hydrogen atom or a methyl group. Also, the bond at both ends represents a single bond to another part in the molecule. }
A negative photosensitive resin composition comprising an ether compound containing in the molecule one or more structural units represented by and a photopolymerization initiator (C).
The negative photosensitive resin composition according to claim 11, wherein the (D) ether compound contains two or more structural units represented by the general formula (1) in a molecule.
The negative photosensitive resin composition according to claim 11 or 12, wherein the one or more protected amino groups is an amino group protected by a tert-butoxycarbonyl group.
The (A) polyimide precursor has the following general formula (2):

Wherein 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 hydrogen It is an atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having a polymerizable group at its end. }
The negative photosensitive resin composition according to any one of claims 11 to 13, comprising a polyimide precursor having a structural unit represented by
In the general formula (2), at least one of R 1 and R 2 has the following general formula (3):

Wherein L 1 , L 2 and L 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer of 2 to 10. The negative photosensitive resin composition according to claim 14, which is a monovalent organic group represented by
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 14 or 15 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (5):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 14 or 15 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (6):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 14 or 15 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{Wherein R 1 , R 2 and n 1 are as defined in the general formula (2), provided that R 1 , R 2 and n 1 in the general formula (5) have the general formula ( 4) R 1 , R 2 and n 1 in 4) are independently selected. }
The negative photosensitive resin composition of Claim 14 or 15 containing both of a polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
A polyimide precursor having a structural unit represented by the following general formula (6):

{Wherein R 1 , R 2 and n 1 are as defined in the general formula (2), provided that R 1 , R 2 and n 1 in the general formula (6) have the general formula ( 4) R 1 , R 2 and n 1 in 4) are independently selected. }
The negative photosensitive resin composition of Claim 14 or 15 containing both of a polyimide precursor which has a structural unit represented by these.
100 parts by mass of the (A) polyimide precursor
0.1 to 30 parts by mass of the (D) ether compound based on 100 parts by mass of the (A) polyimide precursor,
21. The negative photosensitive resin according to any one of claims 11 to 20, which comprises 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor. Resin composition.
(A) polyimide precursor;
(E) One or more amino groups protected by an acid or a base or a thermally deprotected group, and a urethane compound containing at least one hydroxyl group in the molecule; and (C) a photopolymerization initiator , Negative photosensitive resin composition.
The (E) urethane compound has at least one tert-butoxycarbonyl group, benzyloxycarbonyl group or 9-fluorenylmethyloxycarbonyl (Fmoc) group bonded to an aliphatic chain or alicyclic amino group in the molecule. 23. The negative photosensitive resin composition according to claim 22, wherein said photosensitive resin composition comprises
The negative type according to claim 22 or 23, wherein at least one of the nitrogen atoms of the protected one or more amino groups of the (E) urethane compound is at the γ-position or ε-position of the hydroxyl group in the molecule. Photosensitive resin composition.
The negative photosensitive resin composition according to any one of claims 22 to 24, wherein the one or more protected amino groups is an amino group protected by a tert-butoxycarbonyl group.
The (A) polyimide precursor has the following general formula (2):

Wherein 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 hydrogen It is an atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having a polymerizable group at its end. }
The negative photosensitive resin composition according to any one of claims 22 to 25, comprising a polyimide precursor having a structural unit represented by
In the general formula (2), at least one of R 1 and R 2 has the following general formula (3):

Wherein L 1 , L 2 and L 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer of 2 to 10. The negative photosensitive resin composition according to claim 26, which is a monovalent organic group represented by
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 26 or 27 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (5):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 26 or 27 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (6):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
The negative photosensitive resin composition of Claim 26 or 27 containing the polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{Wherein R 1 , R 2 and n 1 are as defined in the general formula (2), provided that R 1 , R 2 and n 1 in the general formula (5) have the general formula ( 4) R 1 , R 2 and n 1 in 4) are independently selected. }
The negative photosensitive resin composition of Claim 26 or 27 containing both of a polyimide precursor which has a structural unit represented by these.
The (A) polyimide precursor has the following general formula (4):

{Wherein, R 1 , R 2 and n 1 are as defined in the general formula (2). }
A polyimide precursor having a structural unit represented by the following general formula (6):

{Wherein R 1 , R 2 and n 1 are as defined in the general formula (2), provided that R 1 , R 2 and n 1 in the general formula (6) have the general formula ( 4) R 1 , R 2 and n 1 in 4) are independently selected. }
The negative photosensitive resin composition of Claim 26 or 27 containing both of a polyimide precursor which has a structural unit represented by these.
The (E) urethane compound is Nα- (tert-butoxycarbonyl) -L-triptophanol, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, or the following chemical formula (1):

The photosensitive resin composition according to any one of claims 22 to 32, which is a urethane compound represented by
100 parts by mass of the (A) polyimide precursor
0.1 to 30 parts by mass of the (E) urethane compound, based on 100 parts by mass of the (A) polyimide precursor,
34. The negative photosensitive resin according to any one of claims 22 to 33, comprising 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor. Resin composition.
A method for producing a polyimide, which cures the negative photosensitive resin composition according to any one of claims 1 to 34.
(1) applying the negative photosensitive resin composition according to any one of claims 1 to 34 on a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the steps of: heat treating the relief pattern to form a cured relief pattern.