JP7787641B2 - Negative photosensitive resin composition and method for producing cured relief pattern using the same - Google Patents

Description

This disclosure relates to a negative-type photosensitive resin composition and a method for producing a cured relief pattern using the same.

Traditionally, polyimide resins, polybenzoxazole resins, phenolic resins, and other resins, which combine excellent heat resistance with electrical and mechanical properties, have been used as insulating materials for electronic components, and for passivation films, surface protection films, and interlayer insulating films for semiconductor devices. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant relief pattern films by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment through curing. Such photosensitive resin compositions have the advantage of enabling significant process reductions compared to conventional non-photosensitive materials.

In recent years, however, the methods of mounting semiconductor devices to printed wiring boards (packaging structures) have also changed in light of improvements in integration density and computing functionality, as well as the need to reduce chip size. The traditional mounting method using metal pins and lead-tin eutectic solder has been replaced by structures in which a polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher-density mounting. Furthermore, structures such as FO (fan-out) have been proposed, in which the surface of a semiconductor chip has multiple redistribution layers with an area larger than the area of the semiconductor chip.

Thermally cyclizable resins, such as polyimide precursor resins, that undergo cyclization by heat can form cured films with excellent physical and chemical properties, but these cyclization reactions require heat treatment at high temperatures (e.g., 350°C). However, when the area of a packaging structure is large, as in the case of the FO described above, the thermal expansion caused by high-temperature heat treatment can lead to warping of the support, breaks in the metal rewiring layer, and destruction of the insulating layer. Therefore, there is a need to reduce the processing temperature. However, lowering the processing temperature can result in a decrease in the chemical resistance of the cured relief pattern.

Patent Document 1 describes adding 35 parts by mass of a radically polymerizable compound per 100 parts by mass of polymer in order to improve the chemical resistance of the cured relief pattern. According to this document, by adding a total of 35 parts by mass of two specific radically polymerizable compounds, it is possible to obtain a cured relief pattern that exhibits good chemical resistance even when cured at a low temperature of 225°C.

International Publication No. 2018/155639 U.S. Pat. No. 5,502,143

However, as described in Patent Document 1, photosensitive resin compositions containing large amounts of radically polymerizable compounds have the problem of easily becoming cloudy when applied to a substrate. Therefore, the present disclosure aims to provide a negative-tone photosensitive resin composition that can be thermally cured at a relatively low temperature, exhibits good chemical resistance, and is less likely to become cloudy when applied, as well as a method for producing a cured relief pattern using the same.

The present inventors have found that the above-mentioned problems can be solved by combining a polyimide precursor and/or a polyimide with a radical polymerizable compound, a surfactant, and a photopolymerization initiator in specific amounts. Examples of embodiments of the present invention are described in the following items [1] to [19].
[1]
100 parts by weight of a polyimide precursor and/or a polyimide;
20 to 150 parts by mass of a radical polymerizable compound;
0.001 to 1 parts by weight of a surfactant;
0.1 to 10 parts by mass of a photopolymerization initiator;
A negative photosensitive resin composition comprising:
[2]
2. The negative photosensitive resin composition according to item 1, wherein the negative photosensitive resin composition contains the polyimide precursor but does not contain the polyimide.
[3]
3. The negative photosensitive resin composition according to item 1 or 2, wherein the surfactant is at least one selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant.
[4]
4. The negative photosensitive resin composition according to any one of items 1 to 3, wherein the surfactant is a fluorine-based surfactant.
[5]
5. The negative photosensitive resin composition according to any one of items 1 to 4, wherein at least one of the radical polymerizable compounds is a radical polymerizable compound having at least one group selected from the group consisting of a hydroxyl group and a urea group.
[6]
6. The negative photosensitive resin composition according to any one of items 1 to 5, wherein the radical polymerizable compound comprises a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound.
[7]
6. The negative photosensitive resin composition according to any one of items 1 to 5, wherein the radical polymerizable compound comprises a nitrogen atom-containing radical polymerizable compound and a nitrogen atom-free radical polymerizable compound.
[8]
The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (1):
In formula (1), _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.
8. The negative photosensitive resin composition according to any one of items 1 to 7, comprising a polyimide precursor having a structural unit represented by the formula:
[9]
In the above general formula (1), at least one of R ₁ and R ₂ is represented by the following general formula (2):
{In formula (2), L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}
Item 9. The negative photosensitive resin composition according to item 8, having a structural unit represented by the following formula:
[10]
The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (3):
{In formula (3), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
10. The negative photosensitive resin composition according to any one of items 1 to 9, comprising a polyimide precursor having a structural unit represented by the formula:
[11]
The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (4):
{In formula (4), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
11. The negative photosensitive resin composition according to any one of items 1 to 10, comprising a polyimide precursor having a structural unit represented by the formula:
[12]
The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (5):
{In formula (5), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
12. The negative photosensitive resin composition according to any one of items 1 to 11, comprising a polyimide precursor having a structural unit represented by the formula:
[13]
The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6):
{In formula (6), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
13. The negative photosensitive resin composition according to any one of items 1 to 12, comprising a polyimide precursor having a structural unit represented by the formula:
[14]
14. The negative photosensitive resin composition according to any one of items 1 to 13, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member.
[15]
15. The negative photosensitive resin composition according to any one of items 1 to 14, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film.
[16]
(1) A step of applying the negative photosensitive resin composition according to any one of items 1 to 15 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
[17]
Item 17. The method for producing a cured relief pattern according to Item 16, wherein the heat treatment in step (4) is a heat treatment at 200° C. or less.
[18]
Item 17. The method for producing a cured relief pattern according to Item 16, wherein the heat treatment in step (4) is a heat treatment at 170°C or lower.
[19]
Item 16. A method for producing a polyimide, comprising curing the negative photosensitive resin composition according to any one of items 1 to 15.

The present disclosure provides a negative-tone photosensitive resin composition that can be thermally cured at a relatively low temperature, exhibits good chemical resistance, and is less likely to become cloudy when applied, as well as a method for producing a cured relief pattern using the same.

<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition of the present disclosure comprises:
100 parts by mass of (A1) a polyimide precursor and/or (A2) a polyimide;
20 to 150 parts by mass of a radical polymerizable compound (B);
0.001 to 1 parts by mass of a surfactant (C);
0.1 to 10 parts by mass of (D) a photopolymerization initiator;
The negative photosensitive resin composition more preferably contains a polyimide precursor, and even more preferably contains a polyimide precursor and does not contain a polyimide.

(A1) Polyimide Precursor The (A1) polyimide precursor is a resin component contained in the negative photosensitive resin composition, and is converted to a polyimide by a thermal cyclization treatment. The structure of the (A1) polyimide precursor is not limited as long as it is a resin that can be used in the negative photosensitive resin composition, but it is preferable that the polyimide precursor is not alkali-soluble. Since the polyimide precursor is not alkali-soluble, high chemical resistance can be obtained.

The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (1).
In formula (1), _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.

In the general formula (1), at least one of R ₁ and R ₂ is a group represented by the following general formula (2):
{In formula (2), L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}
It is preferable that the compound has a structural unit represented by the following formula:

The proportion of hydrogen atoms in _R1 and _R2 in general formula (1) is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, based on the total number of moles of _R1 and _R2 . The proportion of monovalent organic groups represented by general formula (2) in _R1 and _R2 in general formula (1) is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, based on the total number of moles of _R1 and _R2 . It is preferable that the proportion of hydrogen atoms and the proportion of organic groups of general formula (2) be within the above ranges from the viewpoint of photosensitive properties and storage stability.

In general formula (1), _n1 is not limited as long as it is an integer of 2 to 150. From the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition, n1 is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

In general formula (1), the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the _-COOR1 group, the _-COOR2 group, and the -CONH- group are located at the ortho positions relative to each other, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by _X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (20):
{wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} However, the present invention is not limited to these. The structure of _X1 may be one type or a combination of two or more types. The _X1 group having the structure represented by the above formula (20) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

As the _X1 group, among the structures represented by the above formula (20), particularly, those represented by the following formula:
A tetravalent organic group represented by the formula: {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3.} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

In the above general formula (1), the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (21):
{wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} However, the examples are not limited to these. The structure of _Y1 may be one type or a combination of two or more types. A _Y1 group having a structure represented by the above formula (21) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

As the _Y1 group, among the structures represented by the above formula (21), particularly, those represented by the following formula:
A divalent group represented by the formula: {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

In the general formula (2), _L1 is preferably a hydrogen atom or a methyl group, and _L2 and _L3 are preferably hydrogen atoms from the viewpoint of photosensitivity. _m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitivity.

In one embodiment, the polyimide precursor (A1) is represented by the following general formula (3):
{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
It is preferable that the polyimide precursor has a structural unit represented by the following formula:

In general formula (3), at least one of _R1 and _R2 is more preferably a monovalent organic group represented by general formula (2). When the polyimide precursor (A1) contains a polyimide precursor represented by general formula (3), chemical resistance is particularly enhanced.

In one embodiment, the polyimide precursor (A1) is represented by the following general formula (4):
{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
From the viewpoint of thermal properties, it is preferable that the polyimide precursor has a structural unit represented by the following formula:
In general formula (4), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by general formula (2) above.

The (A1) polyimide precursor tends to have particularly high resolution when it contains both a structural unit represented by general formula (3) and a structural unit represented by general formula (4). For example, the (A1) polyimide precursor may contain a copolymer of a structural unit represented by general formula (3) and a structural unit represented by general formula (4), or may be a mixture of a polyimide precursor represented by general formula (3) and a polyimide precursor represented by general formula (4).

In one embodiment, the polyimide precursor (A1) is represented by the following general formula (5):
{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
In the general formula (5), at least one of _R1 and _R2 is more preferably a monovalent organic group represented by the general formula (2). When the polyimide precursor contains the polyimide precursor represented by the general formula (5), chemical resistance is particularly enhanced.

In one embodiment, the polyimide precursor (A1) is represented by the following general formula (6):
{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
In general formula (6), at least one of _R1 and _R2 is more preferably a monovalent organic group represented by general formula (2). When the polyimide precursor (A1) contains the polyimide precursor represented by general formula (6), chemical resistance is particularly enhanced.

(A1) Polyimide Precursor Preparation Method The (A1) polyimide precursor is obtained by first reacting the above-mentioned tetracarboxylic acid dianhydride containing the tetravalent organic group _X1 with a photopolymerizable alcohol having an unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester), and then subjecting the partially esterified tetracarboxylic acid to amide polycondensation with the above-mentioned diamine containing the divalent organic group _Y1 .

Preparation of Acid/Ester Form (A1) Examples of tetracarboxylic acid dianhydrides containing a tetravalent organic group _X1 that are suitably used for preparing a polyimide precursor include the tetracarboxylic acid dianhydride represented by the general formula (20) above, as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid dianhydride, and the like. Examples of suitable dianhydrides include tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. These may be used alone or in combination of two or more.

(A1) Examples of alcohols having a photopolymerizable unsaturated double bond that are suitable for use in preparing the polyimide precursor include 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-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-cyclopropyl acrylate. Examples include cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 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, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

The above-mentioned photopolymerizable alcohols having an unsaturated double bond can also be partially mixed with alcohols not having an unsaturated double bond, such as 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, tetraethylene glycol monoethyl ether, and benzyl alcohol.

As the polyimide precursor, a non-photosensitive polyimide precursor prepared solely from the above-mentioned alcohols that do not have unsaturated double bonds may be used in combination 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 per 100 parts by mass of the photosensitive polyimide precursor.

By stirring, dissolving, and mixing the above-mentioned tetracarboxylic dianhydride and the above-mentioned alcohol in a solvent such as that described below in the presence of a basic catalyst such as pyridine, the esterification reaction of the acid anhydride proceeds, and the desired acid/ester can be obtained. The stirring, dissolving, and mixing can be carried out, for example, at a temperature of 20 to 50°C for 4 to 24 hours.

Preparation of Polyimide Precursor: A suitable dehydration condensation agent is added to and mixed with the above acid/ester compound (typically a solution in a solvent described below) under ice cooling to convert the acid/ester compound into a polyacid anhydride. A diamine containing a divalent organic group _Y1 , dissolved or dispersed in a separate solvent, is then added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. Alternatively, the acid moiety of the above acid/ester compound can be converted into an acid chloride using thionyl chloride or the like, followed by reaction with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

Diamines containing a divalent organic group _Y1 include diamines having a structure represented by the above general formula (21), as well as, 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'-diaminodiphenyl sulfone, biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, Bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfonate Examples of such fluorenes include, but are not limited to, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

After the amide polycondensation reaction is complete, any water-absorbing by-products of the dehydrating condensing agent present in the reaction solution can be filtered off, if necessary. A poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, can then be added to the resulting polymer component to precipitate the polymer component. The polymer can then be purified by repeated redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution can be passed through a column packed with anion and/or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the polyimide precursor (A1), as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in the developer and good relief pattern resolution. 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 monodisperse polystyrenes. It is recommended that standard monodisperse polystyrenes be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko KK.

(A2) Polyimide The (A2) polyimide is an organic solvent-soluble polyimide and is composed of a polycondensate of a tetracarboxylic acid component and an organic diamine component.

The organic diamine component is not particularly limited, but examples include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6 ... nyl)-1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5' -dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)-biphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-(p-phenyleneisopropylidene)bisaniline, 4,4'-(m-phenyleneisopropylidene)bisaniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane Examples of suitable diamines include aromatic diamines such as fluoropropane and 4,4'-bis[4-(4-amino-2-trifluoromethyl)phenoxy]octafluorobiphenyl; aromatic diamines having two amino groups bonded to an aromatic ring and a heteroatom other than the nitrogen atom of the amino groups, such as diaminotetraphenylthiophene; and aliphatic and alicyclic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenediamine, and 4,4'-methylenebis(cyclohexylamine). These may be used alone or in combination. Particularly preferred examples include 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and 1,3-bis(3-aminophenoxy)benzene.

The organic diamine component may further contain an organic diamine having a siloxane bond. The siloxane bond-containing diamine may be a commercially available product, such as those sold by Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Co., Ltd., or Chisso Corporation. Specific examples include KF-8010 (amino group equivalent weight: approximately 450) and X-22-161A (amino group equivalent weight: approximately 840), both manufactured by Shin-Etsu Chemical Co., Ltd.

In addition to the above, the organic diamine component may also include diamines having hydroxyl groups and/or carboxyl groups. The organic diamines having hydroxyl groups and/or carboxyl groups are not particularly limited as long as they have hydroxyl groups and/or carboxyl groups. Preferred examples include diaminophenols such as 2,4-diaminophenol; hydroxybiphenyl compounds such as 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, and 4,4'-diamino-2,2',5,5'-tetrahydroxybiphenyl; 3,3'-diamino-4,4'-dihydroxydiphenylmethane, and 4,4'-diamino-3,3'-dihydroxydiphenyl. Hydroxydiphenylalkanes such as methane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and hydroxydiphenylmethanes such as 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenylmethane; 3,3'-diamino-4,4'-dihydroxydiphenyl ether hydroxydiphenyl ether compounds such as 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, and 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenyl ether; hydroxydiphenyl ether compounds such as 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 4,4'-diamino-2,2'-dihydroxydiphenyl sulfone, and 4,4'-diamino-2,2', Diphenyl sulfone compounds such as 5,5'-tetrahydroxydiphenyl sulfone; bis[(hydroxyphenyl)phenyl]alkane compounds such as 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]propane; bis(hydroxyphenoxy)biphenyl compounds such as 4,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl; bis[(hydroxyphenoxy)phenyl]sulfone compounds such as 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]sulfone diaminobenzoic acids such as 3,5-diaminobenzoic acid; carboxybiphenyl compounds such as 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, and 4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl; 3,3'-diamino-4,4'-dicarboxydiphenylmethane, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, 4,4'-diamino-2 , 2'-dicarboxydiphenylmethane, 2,2-bis[3-amino-4-carboxyphenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoropropane, carboxydiphenylmethanes such as 4,4'-diamino-2,2',5,5'-tetracarboxydiphenylmethane; carboxydiphenylalkanes such as 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3 carboxydiphenyl ether compounds such as 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, and 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether; carboxydiphenyl ether compounds such as 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl sulfone, 4,4'-diamino-2,2'-dicarboxydiphenyl sulfone, and 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether; diphenyl sulfone compounds such as phenyl sulfone; bis[(carboxyphenoxy)phenyl]alkane compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane; bis(carboxyphenoxy)biphenyl compounds such as 4,4'-bis(4-amino-3-carboxyphenoxy)biphenyl; and bis[(carboxyphenoxy)phenyl]sulfone compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone. These may be used alone or in combination of two or more. Other examples of organic diamines having a hydroxyl group and/or a carboxyl group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1-hydroxy-2,4-diaminobenzene, 3,3'-dihydroxybenzidine, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 1,4-bis-(3-hydroxy-4-aminophenoxy)benzene, 2,2-bis(4-amino-3-hydroxyphenyl)propane, biphenyl, Examples of such compounds include bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfide, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,3-diamino-4-carboxybenzene, 1,3-diamino-5-carboxybenzene, and 1,4-diamino-2-carboxybenzene.

The tetracarboxylic acid component used in the present invention is not particularly limited as long as it is a tetracarboxylic acid component. For example, aliphatic or alicyclic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, and bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride; pyromellitic acid dianhydride; 3,3' ,4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxy aromatic tetracarboxylic acid dianhydrides such as 1,3,3a,4,5,9b-hexahydro-2,5-dioxo-3-furanyl)-naphtho[1,3,3a,4,5,9b-hexahydro-2,5-dioxo-3-furanyl] ... 2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), ethylene glycol bis(trimellitic acid monoester anhydride), and bicyclo[2,2,2]-oct-7-ene tetracarboxylic acid dianhydride. These tetracarboxylic acid dianhydrides can be used alone or in combination of two or more.

(A2) Method for Producing Polyimide The polyimide in the negative-type photosensitive resin composition of the present disclosure can be synthesized by mixing and heating a tetracarboxylic dianhydride and a diamine in an organic solvent in the presence of an acid catalyst. The water produced can be removed from the reaction system by azeotropy with toluene, xylene, decalin, or the like mixed in the solvent.

Polyimide can be produced using a catalyst system that utilizes the equilibrium reaction of lactone, base, and water as an acid catalyst. For example, a polyimide solution can be obtained by heating to 140-180°C using the [acid group] + [base] formed in the equilibrium reaction of [lactone] + [base] + [water] = [acid group] + [base] as a catalyst. The water produced can be removed from the reaction system by azeotroping with toluene or other solvents. Once imidization is complete, the [acid group] + [base] reverts to lactone, base, and water, losing its catalytic activity and can be removed from the reaction system along with toluene or other solvents. Because the polyimide solution produced by this method does not contain the above-mentioned catalytic substance after the reaction, it is a high-purity polyimide solution that can be used industrially as is.

In addition to toluene, polar organic solvents can be used as reaction solvents for the imidization reaction. Examples of these organic solvents include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, tetramethylurea, and γ-butyrolactone. These solvents can be used alone or in the form of a mixture. An appropriate amount of an aliphatic alcohol, such as isopropyl alcohol, can also be mixed with these solvents.

In addition to the above reaction solvents, examples of diluents include ketone-based solvents such as acetone, cyclohexane, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve-based solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and butyl cellosolve acetate; ester-based solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, and methyl 3-methoxypropionate; and cyclic ether compounds such as dioxane and dioxolane.

The lactone is preferably gamma-valerolactone, and the base is preferably pyridine and/or methylmorpholine. A known method for producing polyimides using a two-component catalyst containing a lactone and a base is described, for example, in U.S. Pat. No. 5,502,143.

The mixing ratio (tetracarboxylic dianhydride/diamine) between the tetracarboxylic dianhydride and diamine used in the imidization reaction is preferably 0.8 to 1.3, more preferably 0.95 to 1.05, in molar ratio. The concentration of the acid dianhydride in the entire reaction mixture at the start of the reaction is preferably approximately 4 to 16% by mass. When a lactone is added as a catalyst system, the lactone concentration is preferably approximately 0.2 to 0.6% by mass. The base concentration is preferably approximately 0.3 to 0.9% by mass. The concentration of the azeotropic solvent, such as toluene, is preferably approximately 6 to 15% by mass. The heating temperature is preferably 140°C to 200°C, more preferably 150°C to 180°C. The reaction time is not particularly limited and varies depending on the molecular weight of the polyimide to be produced, but is usually approximately 2 to 10 hours. The reaction is preferably carried out with stirring.

Polyimides may be composed of one type of tetracarboxylic dianhydride and one type of organic diamine, but they may also be copolymers of three or more components, with two or more types of at least one of the tetracarboxylic dianhydrides and organic diamines. This makes it possible to impart desired properties, such as optical transparency, high resolution, and adhesion to the substrate. Block copolymers are preferable to random copolymers in terms of copolymer structure, as it is easier to control the properties of the produced polyimide as desired, making it easier to modify the polyimide.

By carrying out the imidization reaction in two successive stages using different tetracarboxylic dianhydrides and/or different diamines, it is possible to produce a block copolymer polyimide. Conventional methods for producing polyimides via polyamic acid have only been able to produce random copolymers. This method allows for the production of block copolymer polyimides by selecting any acid anhydride and/or diamine component, thereby imparting the desired properties and functions described above to the polyimide.

A preferred method for producing block polyimide copolymers involves using an acid catalyst generated from the above lactone and a base to prepare a polyimide oligomer by converting a large amount of either the diamine or the tetracarboxylic dianhydride, and then adding the diamine and/or the tetracarboxylic dianhydride to carry out two-stage polycondensation. The molar ratio of the tetracarboxylic dianhydride to the diamine (tetracarboxylic dianhydride/diamine) is preferably 0.8 to 1.3.

Block copolymer polyimides containing alicyclic tetracarboxylic dianhydrides, diaminosiloxanes, and aliphatic disulfides are particularly used as photolithography materials that exhibit submicron optical resolution.

In addition to polyimides produced from the above compositions, amorphous aliphatic or alicyclic block copolymer polyimides having strained groups, such as spirocyclic groups, may also be used. This allows the block copolymer polyimides to have high and precise resolution.

The molecular weight of the polyimide, as measured by gel permeation chromatography using the weight-average molecular weight converted into polystyrene, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. A weight-average molecular weight of 8,000 or higher provides good mechanical properties, while a weight-average molecular weight of 150,000 or lower provides good dispersibility in the developer and good relief pattern resolution. 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 monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from Showa Denko's organic solvent-based standard sample, STANDARD SM-105.

When producing polyimides, it is also possible to add acid anhydrides such as phthalic anhydride or aromatic amines such as aniline to the reaction system as end terminators.

(B) Radical Polymerizable Compound The negative photosensitive resin composition of the present disclosure contains a radical polymerizable compound (B) to improve the chemical resistance of the cured relief pattern. To obtain good chemical resistance, the composition contains 20 parts by mass or more of the radical polymerizable compound (B) per 100 parts by mass of the polyimide precursor (A1) and/or the polyimide (A2) combined, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. From the viewpoint of patterning properties, the amount of the radical polymerizable compound (B) is 150 parts by mass or less, preferably 100 parts by mass or less, and more preferably 60 parts by mass or less.

When the negative-type photosensitive resin composition contains the polyimide precursor (A1) but does not contain the polyimide (A2), the amount of the radical polymerizable compound (B) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. When the negative-type photosensitive resin composition contains the polyimide precursor (A1) but does not contain the polyimide (A2), the amount of the radical polymerizable compound (B) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 60 parts by mass or less, from the viewpoint of patterning properties. When the negative-type photosensitive resin composition does not contain the polyimide precursor (A1) but does contain the polyimide (A2), the amount of the radical polymerizable compound (B) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and even more preferably 100 parts by mass or more, from the viewpoint of patterning properties. When the negative-type photosensitive resin composition does not contain the polyimide precursor (A1) and contains the polyimide (A2), the amount of the radical polymerizable compound (B) is preferably 150 parts by mass or less, more preferably 130 parts by mass or less, and even more preferably 110 parts by mass or less, from the viewpoint of the mechanical properties of the film.

The radical polymerizable compound is not particularly limited as long as it is a compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, but is preferably a (meth)acrylic compound, for example, a compound represented by the following general formula (7):
{In formula (7), X ₁₁ is an organic group, L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and n ₁₁ is an integer of 1 to 10.}

Radically polymerizable compounds include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, di-, or triacrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylate; diacrylate and dimethacrylate of 1,4-butanediol; and diacrylate and dimethacrylate of 1,6-hexanediol. acrylate, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds can be mentioned.

More specifically, the radical polymerizable compound is a compound represented by the following formula:
Examples of the compound include, but are not limited to, compounds represented by the following formula:

In this specification, when a radical polymerizable compound has one radical polymerizable group, it is referred to as monofunctional; when it has two or more radical polymerizable groups, it is referred to as x-functional group, according to the number x of radical polymerizable groups. Difunctional or higher functional groups are sometimes collectively referred to as polyfunctional. The radical polymerizable compound may be monofunctional, or may be difunctional or higher. From the viewpoint of chemical resistance, the radical polymerizable compound is preferably trifunctional or higher, more preferably tetrafunctional or higher, and even more preferably hexafunctional or higher. On the other hand, from the viewpoint of elongation at break, it is preferable that the radical polymerizable compound be decafunctional or lower.

The molecular weight of the radically polymerizable compound is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. The upper limit is preferably 1000 or less, and even more preferably 800 or less. By keeping it within the above range, chemical resistance and patterning properties are improved.

It is preferable that at least one of the (B) radically polymerizable compounds is a radically polymerizable compound having at least one hydroxyl group or urea group.

The radical polymerizable compound having a hydroxyl group in the molecule includes a compound represented by the following general formula (8):
{In formula (8), X ₁₁ is an organic group, and L ₁₁ , L ₁₂ and L ₁₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. _{n 11} is an integer of 1 to 10, and n ₁₂ is an integer of 1 to 10.}

In the above formula (8), it is preferable that L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms from the viewpoint of radical reactivity. More specifically, it is preferable that L 11 is a hydrogen atom or a methyl group, and L 12 and L 13 are hydrogen atoms from the viewpoint of radical reactivity.
Examples include, but are not limited to, compounds represented by the formula: [0033] Having a hydroxyl group in the molecular structure provides particularly good chemical resistance. The number of hydroxyl groups in the molecular structure is preferably one or more, and more preferably two or more. The upper limit is preferably 10 or less, more preferably six or less, and even more preferably three or less. By setting the number within the above range, good chemical resistance and adhesion to the substrate are achieved.

The radical polymerizable compound having a urea group in the molecule is represented by the following general formula (9):
{In formula (9), X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ each independently represent a hydrogen atom, a monovalent organic group having a group represented by the following general formula (10), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and at least one of X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ is a monovalent organic group having a group represented by the following general formula (10).}
{In formula (10), L ₁₁ , L ₁₂ and L ₁₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.}
In the above formula (10), it is preferable that L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms from the viewpoint of radical reactivity. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

In formula (9), when X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ are monovalent organic groups having 1 to 20 carbon atoms, which may contain a heteroatom, it is more preferable that they contain an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it is preferable that the number of carbon atoms is 1 to 10, and more preferably 3 to 10. X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ in formula (9) may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. When X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. From the viewpoint of forming a hydrogen bond with other molecules, it is preferable that at least one of X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferable that the number of hydrogen atoms in X ₂₀ , X ₂₁ , X ₂₂ and X ₂₃ is 2 or less.
Examples of the compound are compounds represented by the following formula:

The radical polymerizable compound (B) preferably has at least one hydroxyl group and at least one urea group in the molecule. The radical polymerizable compound having at least one hydroxyl group and at least one urea group in the molecule is, for example, a compound represented by the following general formula (11):
{In formula (11), X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ each independently represent a hydrogen atom, a monovalent organic group having a group represented by the following general formula (12), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and at least one of X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ is a monovalent organic group having a group represented by the following general formula (12), and at least one is a hydroxyl group.}
{In formula (12), L ₁₁ , L ₁₂ and L ₁₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.}
In the above formula (12), it is preferable that L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms from the viewpoint of radical reactivity.

In the formula (11), when X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ are monovalent organic groups having 1 to 20 carbon atoms, which may contain a heteroatom, it is more preferable that they contain an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it is preferable that the number of carbon atoms is 1 to 10, and more preferably 3 to 10. X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ in the formula (11) may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. When X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. From the viewpoint of forming a hydrogen bond with other molecules, it is preferable that at least one of X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferable that the number of hydrogen atoms in X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ is 2 or less.
Examples of the compound are compounds represented by the following formula:

Of the (B) radically polymerizable compounds, the radically polymerizable compound having a urea group can be produced by any method, but can be obtained, for example, by reacting an isocyanate compound having a radically polymerizable group with an amine-containing compound. If the amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, a portion of the isocyanate compound may contain a compound that has reacted with the functional group such as a hydroxyl group.

(B) The radical polymerizable compound may be used alone, but it is preferable to use a mixture of two or more types. Using a mixture of two or more radical polymerizable compounds improves chemical resistance and in-plane film thickness uniformity. The reason for this improved in-plane film thickness uniformity is not clear and is not limited by theory, but it is thought that when a large amount of only one type of radical polymerizable compound is added, microphase separation occurs with the polyimide precursor component in the varnish, whereas using a mixture of two or more types suppresses microphase separation. For the above reasons, when a radical polymerizable compound is used alone, it is preferably used in an amount of 60 parts by mass or less, and more preferably 40 parts by mass or less, per 100 parts by mass of polyimide precursor.

When two or more radically polymerizable compounds are used in combination, from the viewpoint of controlling the crosslink density, it is preferable that the number of types be six or less, and more preferably four or less.

When multiple radical polymerizable compounds are used in combination, it is preferable that at least one of the multiple radical polymerizable compounds has a different number of functional groups. From the viewpoints of chemical resistance and in-plane film thickness uniformity, it is more preferable that the radical polymerizable compounds contain at least one monofunctional radical polymerizable compound and one polyfunctional radical polymerizable compound. When three or more radical polymerizable compounds are used, it is sufficient that at least one of them has a different number of functional groups, but it is preferable that all of the radical polymerizable compounds have different numbers of functional groups. When multiple radical polymerizable compounds are used, it is preferable that at least one is a monofunctional radical polymerizable compound from the viewpoint of breaking elongation.

When using a mixture of two or more radically polymerizable compounds, it is preferable to contain at least one nitrogen-atom-containing radically polymerizable compound and one non-nitrogen-atom-containing radically polymerizable compound. The nitrogen-atom-containing radically polymerizable compound is preferably a urea group-containing radically polymerizable compound. Nitrogen-atom-containing radically polymerizable compounds are capable of forming strong hydrogen bonds and therefore have excellent chemical resistance. From the perspective of simplifying the hydrogen bond network and improving solubility, it is preferable to use only one type of nitrogen-atom-containing radically polymerizable compound when adding it.

(C) Surfactant The negative-type photosensitive resin composition of the present disclosure contains a (C) surfactant to prevent clouding during application. To exhibit a sufficient clouding prevention effect, the (C) surfactant is contained in an amount of 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of the (A1) polyimide precursor and/or (A2) polyimide combined. On the other hand, if the surfactant is contained in excess, the in-plane film thickness uniformity after application deteriorates. Therefore, the amount of the (C) surfactant is 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, and even more preferably 0.05 parts by mass or less.

While the reason why a surfactant suppresses cloudiness is unclear, the present inventors believe it to be as follows: In one embodiment, a photosensitive resin composition containing a large amount of a radically polymerizable compound is more likely to absorb moisture from the air when spin-coated. This moisture absorption causes the polyimide precursor to become insoluble in the solvent, resulting in precipitation. The inclusion of a surfactant at this time is thought to form a surfactant-derived layer on the top of the film surface, thereby suppressing moisture absorption and, ultimately, cloudiness. Alternatively, in one embodiment, a photosensitive resin composition containing a large amount of a radically polymerizable compound is thought to cause phase separation between the polyimide precursor and the radically polymerizable compound due to solvent evaporation or differences in compatibility when spin-coated, resulting in cloudiness. The inclusion of a surfactant at this time is thought to form a surfactant-derived layer on the top of the film surface, suppressing solvent evaporation or improving compatibility, thereby suppressing cloudiness.

Surfactants include fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants.

There are no particular limitations on fluorosurfactants, as long as they contain a fluorine atom in the molecule. Examples of fluorosurfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl alcohols, perfluoroalkyl alkylene oxide adducts, and perfluoroalkyl phosphate esters. More specifically, these surfactants are available under the trade names Megafac F-114, Megafac F-251, Megafac F-253, Megafac F-281, Megafac F-410, Megafac F-430, Megafac F-477, Megafac F-510, Megafac F-551, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-557, Megafac F-558, Megafac F-559, Megafac F-560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-564, Megafac F-565, Megafac F-566, Megafac F-567, Megafac F-568, Megafac F-569, Megafac F-566, Megafac F-569, Megafac F-560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-564, Megafac F-565, Megafac F-566, Megafac F-567, Megafac F-568, Megafac F-569, Megafac F-569, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-564, Megafac F-565, Megafac F-566, Megafac F-567 F-558, Megafac F-559, Megafac F-560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-565, Megafac F-568, Megafac F-569, Megafac F-570, Megafac F-572, Megafac F-574, Megafac F-575, Megafac F-576, Megafac R-40, Megafac R-40-LM, Megafac R-41, Megafac R-94, Megafac RS-56, Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-78, Megafac RS-90, Megafac DS-21 (all manufactured by DIC Corporation), FC-4430, FC-4432 (all manufactured by 3M Japan Ltd.), Surflon S-211, Surflon S-221, Surflon S-231, Surflon S-232, Examples include Surflon S-233, Surflon S-241, Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-431, Surflon S-386, Surflon S-611, Surflon S-647, Surflon S-651, Surflon S-653, Surflon S-656, Surflon S-658, Surflon S-693, Surflon S-CFJ, and Surflon FPE-50 (all manufactured by AGC Seimi Chemical Co., Ltd.).

There are no particular limitations on the silicone surfactant, as long as it has a disiloxane structure as a non-polar moiety. Examples of silicone surfactants include polyether-modified silicones, such as linear polyether-modified silicones, linear alkyl-co-modified polyether-modified silicones, branched polyether-modified silicones, and branched alkyl-co-modified polyether-modified silicones. More specifically, these include, by trade name, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP-341, KP-104, KP-110, and KP-112 (all manufactured by Shin-Etsu Chemical Co., Ltd.); DB E-224, DBE-621, DBE-712, DBE-814, DBE-821, DBE-921, DBP-732, YAD-122, YBD-125, YMS-T31, CMS-626, CMS-222, DBP-534, CMS-832, DBP-C22, QMS-435 , ABP-263, DMS-R05, DMS-R11, DMS-R18, DMS-R22, DMS-R31 (all manufactured by Gelest); BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315 N, BYK-320, BYK-322, BYK-323, BYK-325 N, BYK-326, BYK-327, BYK-330, BYK-331, BYK-332, BYK-333, BYK-342, BYK-345, BYK-34 6, BYK-347, BYK-348, BYK-349, BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358 N, BYK-359, BYK-360 P, BYK-361 N, BYK-364 P, BYK-366 P, BYK-368 P, BYK-370, BYK-375, BYK-377, BYK-378, BYK-381, BYK-390, BYK-392, BYK-394, BYK-399, BYK-UV 3500, BYK-UV 3505, BYK-UV 3510, BYK-UV 3530, BYK-UV 3535, BYK-UV 3570, BYK-UV 3575, BYK-UV 3576 (all manufactured by BYK Japan); Newcol 2302, Newcol 2303, Newcol 2305, Newcol 2307, Newcol 2308, Newcol 2308-HEN, Newcol 2310, Newcol 2312, Newcol 2314, Newcol 2318, Newcol 2320, Newcol 2327(20), Newcol 2330, Newcol 2344, Newcol 2327(20), Newcol 2330, Newcol 2344, Newcol 2327(20), Newcol 2327, ... Examples include Nucol 2360, Nucol 2399-S, and Nucol 2399-S (25) (all manufactured by Nippon Nyukazai Co., Ltd.); DMC6038, OW1500, SPG128VP, L03, L033, L053, and L066 (all manufactured by Wacker Asahi Kasei Silicone Co., Ltd.); and SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (all manufactured by Dow Corning Toray Co., Ltd.).

The surfactant may have a crosslinkable group within the molecule. Examples of such surfactants include silicone surfactants that have a crosslinkable group within the molecule, and fluorine-based surfactants that have a crosslinkable group within the molecule. Examples of crosslinkable groups include thermally crosslinkable groups such as epoxy groups, N-methylolamide groups, oxazoline groups, and allyl groups, as well as ultraviolet (UV) crosslinkable groups such as vinyl groups, (meth)acryloyl groups, and epoxy groups. More specific examples of surfactants having a crosslinkable group in the molecule include, by trade name, Megafac RS-75-A, Megafac RS-72-K, Megafac RS-75-NS, Megafac RS-78, Megafac RS-90, and Megafac RS-56 (all manufactured by DIC Corporation); and BYK-UV3500, BYK-UV3505, BYK-UV3530, BYK-UV3570, BYK-UV3575, and BYK-UV3576 (all manufactured by BYK-Chemie).

The surfactant may be one in which the fluorine-containing group is eliminated by heat treatment. An example of such a surfactant is Megafac DS-21 (manufactured by DIC Corporation).

From the viewpoint of compatibility with the varnish, (C) the surfactant is preferably at least one selected from the group consisting of fluorine-based surfactants and silicone-based surfactants, and from the viewpoint of preventing clouding during application and electrical insulation, a fluorine-based surfactant is even more preferable.

(D) Photopolymerization Initiator The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples thereof include benzophenone derivatives such as benzophenone, o-benzoylbenzoic acid methyl, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 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, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Of the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

The amount of the (D) photopolymerization initiator is 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total of the (A1) polyimide precursor and/or the (A2) polyimide. The amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning ability, and 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

The negative-type photosensitive resin composition may further contain components other than the above components (A1) to (D). Examples of components other than components (A1) to (D) include, but are not limited to, thermal base generators, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organotitanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and polymerization inhibitors.

Thermal Base Generator The negative photosensitive resin composition may contain a thermal base generator. A thermal base generator is a compound that generates a base upon heating. By including a thermal base generator, imidization of the photosensitive resin composition can be further promoted.

Examples of thermal base generators include, but are not limited to, amine compounds protected by a tert-butoxycarbonyl group, or the thermal base generators disclosed in WO 2017/038598. However, the present invention is not limited to these, and other known thermal base generators can also be used.

Amine compounds protected by a tert-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol diamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ether Examples of such tert-butoxycarbonyl compounds include, but are not limited to, tert-butoxycarbonyl 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, 1,11-diamino-3,6,9-trioxaundecane, and compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group.

The amount of the thermal base generator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the (A1) polyimide precursor and/or (A2) polyimide. The amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization-accelerating effect, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition.

Solvent Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyro. Lactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene 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. Among these, from the viewpoints of resin solubility, resin composition stability, and substrate adhesion, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

Among such solvents, those that completely dissolve the resulting polymer are particularly preferred, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone. One type of solvent may be used, or two or more types may be mixed together.

The amount of solvent used in the negative-type photosensitive resin composition is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of the total of the polyimide precursor (A1) and/or the polyimide (A2).

Nitrogen-containing heterocyclic compound When a cured film is formed on a substrate made of copper or a copper alloy using a negative-tone photosensitive resin composition, the negative-tone photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound to suppress discoloration of the copper. Examples of the nitrogen-containing heterocyclic compound include an azole compound and a purine derivative.

Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, Examples of benzotriazole include 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-tetrazole, and 1-methyl-1H-tetrazole.

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

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

When the negative-tone photosensitive resin composition contains an azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total of the (A1) polyimide precursor and/or (A2) polyimide, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative-tone photosensitive resin composition is formed on copper or a copper alloy, while when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

Hindered Phenol Compounds To inhibit discoloration on copper surfaces, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-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'-hexamethylenebis(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, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and the like.

Examples of hindered phenol compounds include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-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, and 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2 ,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-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)- Examples of the hydroxybenzoates include, but are not limited to, 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, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. 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 is particularly preferred.

The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the combined total of the (A1) polyimide precursor and/or (A2) polyimide, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound is 0.1 part by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

Organotitanium Compound The negative photosensitive resin composition may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at low temperatures. Usable organotitanium 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 organotitanium compounds are shown below as I) to VII).
I) As the titanium chelate compound, a titanium chelate having two or more alkoxy groups is more preferred, as this improves the storage stability of the negative photosensitive resin composition and allows for the formation of a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.
II) Examples of tetraalkoxytitanium compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}].
III) Examples of titanocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.
IV) Examples of monoalkoxytitanium compounds include titanium tris(dioctylphosphate)isopropoxide and titanium tris(dodecylbenzenesulfonate)isopropoxide.
V) Examples of titanium oxide compounds include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), and phthalocyanine titanium oxide.
VI) Titanium tetraacetylacetonate compounds include, for example, titanium tetraacetylacetonate.
VII) Examples of titanate coupling agents include isopropyl tridodecylbenzenesulfonyl titanate.

Among these, it is preferable that the organic titanium compound be at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, as this provides better chemical resistance. 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 are particularly preferred.

When an organotitanium compound is added, the amount added is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the combined total of (A1) polyimide precursor and/or (A2) polyimide. When the amount added is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount is 10 parts by mass or less, excellent storage stability is achieved.

Adhesion Aid In order to improve the adhesion between a film formed using the negative photosensitive resin composition and a substrate, the negative photosensitive resin composition may optionally contain an adhesion aid. Examples of the adhesion aid include 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 ]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride and other silane coupling agents, and aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate and other aluminum-based adhesion aids.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the amount of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the total of the (A1) polyimide precursor and/or (A1) polyimide.

Silane coupling agents include, but are not limited to, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxy Examples include mercaptomethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltrippropoxysilane.

Silane coupling agents include, but are not limited to, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS3610, manufactured by Azmax Corporation: product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: product 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-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (trade name, manufactured by Azmax Corporation) Examples include m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: product name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: product name SLA0599.2).

Examples of silane coupling agents include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetra Tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenyl silanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol Examples of such silanol include, but are not limited to, phenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

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

When a silane coupling agent is used, the amount added is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of the polyimide precursor (A1) and/or the polyimide (A2).

Sensitizer The negative photosensitive resin composition may optionally contain a sensitizer to improve 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, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

When the photosensitive resin composition contains a sensitizer to improve photosensitivity, the amount of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the total of the polyimide precursor (A1) and/or the polyimide (A2).

Polymerization Inhibitor The negative photosensitive resin composition may optionally contain a polymerization inhibitor to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition, particularly during storage in the form of a solution containing a solvent. Examples of polymerization inhibitors that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

<<Method for producing a cured relief pattern>>
The method for producing a cured relief pattern includes the steps of: (1) applying the negative photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

(1) Resin Layer Formation Step In this step, a negative photosensitive resin composition is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater, etc., can be used.

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

(3) Relief Pattern Forming Step In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of adjusting the shape of the relief pattern, etc.

The developer used for development is preferably, for example, a good solvent for the negative-tone photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative-tone photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination.

(4) Cured Relief Pattern Formation Step In this step, the relief pattern obtained by the development described above is heat-treated to dissolve the photosensitive component and imidize the polyimide precursor (A1), thereby converting it into a cured relief pattern composed of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is preferably 200°C or less, more preferably 180°C or less, and even more preferably 170°C or less. Air or an inert gas such as nitrogen or argon can also be used as the atmospheric gas during heat curing.

<Polyimide>
Polyimide can be produced by curing a negative-type photosensitive resin composition. Therefore, the present disclosure also provides a method for producing polyimide, which includes curing the negative-type photosensitive resin composition described above. The imidization rate of the polyimide is preferably 80% to 100%. The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula:
{In the above general formula, X ₁ and Y ₁ are the same as X ₁ and Y ₁ in general formula (1), and m is a positive integer.}
For the same reason, the preferred X ₁ and Y ₁ in general formula (1) are also preferred in polyimides having a structure represented by the above general formula. In the above general formula, the number m of repeating units is not particularly limited, but may be an integer of 2 to 150.

Semiconductor Device
The present disclosure also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. Therefore, the present disclosure can also provide a semiconductor device having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. The present disclosure can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-described method for producing a cured relief pattern as part of its process. A semiconductor device can be produced by forming the cured relief pattern formed by the method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

《Display device》
The present disclosure also provides a display device including a display element and a cured film disposed on the display element, the cured film having the cured relief pattern described above. The cured relief pattern may be laminated directly on the display element or may be laminated via another layer. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

The negative-tone photosensitive resin composition is preferably a negative-tone photosensitive resin composition for forming insulating members or interlayer insulating films. In addition to being applied to semiconductor devices such as those described above, negative-tone photosensitive resin compositions are also useful for applications such as interlayer insulating films in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

<<Measurement and Evaluation Methods>>
(1) Weight-average molecular weight The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Showa Denko Shodex KD-806M, two in series, or
Shodex 805M/806M series manufactured by Showa Denko K.K. Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K.
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 A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film approximately 7.5 μm thick. Using a test pattern mask, this coating film was irradiated with i-rays at an energy of 50 to 650 mJ/ ^cm² using a Prisma GHI (manufactured by Ultratech Co., Ltd.). The coating was then spray-developed using cyclopentanone as a developer with a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) for a time equal to 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by a 10-second rotational spray rinse with propylene glycol methyl ether acetate, yielding a relief pattern on Cu. The wafer with the relief pattern formed on Cu was then heat-treated in a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) for 2 hours under a nitrogen atmosphere at the temperature shown in Table 1, yielding a cured relief pattern of resin approximately 4 to 7 μm thick on Cu.

(3) Evaluation of Chemical Resistance The relief pattern prepared by the method of (2) above was mixed with the following weight ratio:
Dimethyl sulfoxide: 98% by weight
Tetramethylammonium hydroxide pentahydrate: 2% by weight
The film was immersed in the chemical solution mixed in step 1 heated to 50°C for 10 minutes, washed with running water for 30 minutes, and air-dried. The film surface was then visually observed with an optical microscope to evaluate chemical resistance based on the presence or absence of damage caused by the chemical solution, such as cracks, and/or the rate of change in film thickness before and after chemical treatment. Chemical resistance was evaluated based on the following criteria.
A: No cracks or the like occurred, and the film thickness change rate was less than 5%. B: No cracks or the like occurred, and the film thickness change rate was 5% or more and less than 10%. C: No cracks or the like occurred, and the film thickness change rate was 10% or more and less than 15%. D: Cracks or the like occurred, or the film thickness change rate was 15% or more.

(4) Evaluation of Whitening Opacity Upon Application The film immediately after spin coating by the method described in (2) above was visually inspected and the degree of whitening opacity was evaluated. The evaluation criteria are as follows:
A: No cloudiness was observed.
B: Slight cloudiness was observed only on the outer periphery within 4 cm from the wafer edge, which was not visible when viewing the wafer from directly above (90°) and was visible only when viewing from an angle of approximately 20° to 60°.
C: White turbidity was observed only on the outer periphery within 4 cm from the wafer edge, which was visible when the wafer was viewed from directly above (90°).
D: White turbidity was observed in areas other than the peripheral area within 4 cm from the wafer edge.

(5) Evaluation of in-plane film thickness uniformity The in-plane film thickness uniformity of the coating film obtained after spin coating and pre-baking using the method described in (2) above was evaluated. Film thickness was measured using a VM-2110 manufactured by Dai-Nippon Screen Mfg. Co., Ltd. Measurements were taken at a total of 88 points, including the center of the wafer and at 66 mm and 1.5 mm intervals to the left and right of the center, and the difference between the maximum and minimum values was taken as the in-plane film thickness uniformity, which was evaluated according to the following criteria.
A: Less than 0.1 B: 0.1 or more and less than 0.5 C: 0.5 or more and less than 1.0 D: 1.0 or more

<Production Examples of Polyimide Precursors and Polyimides>
Preparation Example 1: Synthesis of (A1) Polyimide Precursor A1-1 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone, and the mixture was stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the reaction ceased to generate heat, 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) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes with stirring, followed by a suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone with stirring over 30 minutes. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 mL of γ-butyrolactone. 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 produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum-dried to obtain a powdered polymer (Polyimide Precursor A1-1). The molecular weight of Polyimide Precursor A1-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight-average molecular weight (Mw) was 21,000.

Production Example 2: Synthesis of (A1) Polyimide Precursor A1-2 A polymer (polyimide precursor A1-2) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The molecular weight of polyimide precursor A1-2 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 24,000.

Production Example 3: Synthesis of (A1) Polyimide Precursor A1-3 A polymer (polyimide precursor A1-3) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of polyimide precursor A1-3 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 19,000.

Production Example 4: Synthesis of (A1) Polyimide Precursor A1-4 A polymer (polyimide precursor A1-4) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of polyimide precursor A1-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

Production Example 5: Synthesis of (A1) Polyimide Precursor A1-5 A polymer (polyimide precursor A1-5) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of BPDA were used instead of 155.1 g of ODPA in Production Example 1. The molecular weight of polyimide precursor A1-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

Production Example 6: Synthesis of (A2) Polyimide A2-1 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA), 11.2 g of 4,4'-diaminodiphenyl sulfone, and 11.2 g of 3,3'-diaminodiphenyl sulfone were placed in a 1 L separable flask, and 125 g of γ-butyrolactone was added. 17 g of toluene was added dropwise with stirring. The mixture was then heated to 185°C under a nitrogen atmosphere and stirred for 2 hours. During the reaction, the toluene-water azeotrope was removed, yielding a 30% polyimide solution. The weight-average molecular weight of the polyimide A2-1 thus obtained was 25,000.

<<Production Example of Radically Polymerizable Compound>>
Production Example 7: Synthesis of (B) Radically Polymerizable Compound B-6 60.4 g (0.25 mol) of di-n-octylamine was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K., product name: Karenz MOI) and 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 5 hours. Thereafter, the tetrahydrofuran was distilled off using a rotary evaporator, yielding radically polymerizable compound B-7.

Production Example 8: Synthesis of (B) Radically Polymerizable Compound B-7 26.3 g (0.25 mol) of diethanolamine was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K., product name: Karenz MOI) and 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 5 hours. Thereafter, the tetrahydrofuran was distilled off using a rotary evaporator, yielding radically polymerizable compound B-7.

Examples and Comparative Examples
Example 1
A photosensitive resin composition was prepared using polyimide precursor A-1 by the following method, and the prepared composition was evaluated. 100 g of (A1) polyimide precursor A1-1, 10 g of (B) radical polymerizable compounds B-1 and B-7, 20 g of (B), 0.01 g of (C) surfactant C-1, and 3 g of (D) photopolymerization initiator D-1 were dissolved in a mixed solvent of 80 g of γ-butyrolactone (hereinafter referred to as GBL) and 20 g of dimethyl sulfoxide (hereinafter referred to as DMSO). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding the required amount of a GBL:DMSO = 80:20 solution, and a photosensitive resin composition was obtained. The composition was evaluated according to the method described above. The results are shown in Table 1.

Examples 2 to 31 and Comparative Examples 1 to 3
Photosensitive resin compositions similar to those in Example 1 were prepared, except that they were prepared at the blending ratios shown in Tables 1 and 2, and were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

The (A1) polyimide precursor, (A2) polyimide, (B) radical polymerizable compound, (C) surfactant, and (D) photopolymerization initiator listed in Tables 1 and 2 are as follows. When (A2) polyimide was used, the photosensitive resin composition was prepared taking into account the amount of GBL contained.

A1-1: Polyimide precursor described in Production Example 1 A1-2: Polyimide precursor described in Production Example 2 A1-3: Polyimide precursor described in Production Example 3 A1-4: Polyimide precursor described in Production Example 4 A1-5: Polyimide precursor described in Production Example 5 A2-1: Polyimide described in Production Example 6

B-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.):
B-2: NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.):
B-3: NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.):
B-4: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
B-5: NK Ester A-TMM-3L (manufactured by Shin-Nakamura Chemical Co., Ltd.):
(Contains approximately 55% of the following structure)
B-6: Compound described in Production Example 7:
B-7: Compound described in Production Example 8:

C-1: Megafac F-557 (manufactured by DIC Corporation): Fluorine-based surfactant C-2: Megafac F-554 (manufactured by DIC Corporation): Fluorine-based surfactant C-3: Megafac F-556 (manufactured by DIC Corporation): Fluorine-based surfactant C-4: Megafac F-447 (manufactured by DIC Corporation): Fluorine-based surfactant C-5: Megafac R-40 (manufactured by DIC Corporation): Fluorine-based surfactant C-6: KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.): Silicone-based surfactant C-7: KP-323 (manufactured by Shin-Etsu Chemical Co., Ltd.): Silicone-based surfactant C-8: KP-110 (manufactured by Shin-Etsu Chemical Co., Ltd.): Silicone-based surfactant

D-1:OXE-01
D-2:OXE-02
D-3: PBG-305
D-4:PBG-3057

As shown in Table 1, the negative-type photosensitive resin composition of Example 1 received an A rating for chemical resistance, a B rating for cloudiness during application, and a B rating for in-plane film thickness uniformity. All of the photosensitive resin compositions of Examples 2 to 31 received a C or higher rating for chemical resistance, cloudiness during application, and in-plane film thickness uniformity. In Comparative Example 1, a large amount of film dissolved in the chemical solution, resulting in a D rating for chemical resistance. In Comparative Example 2, in-plane film thickness uniformity was poor, resulting in a D rating. In Comparative Example 3, cloudiness occurred on the front surface of the film during application, resulting in a D rating.

By using the photosensitive resin composition of the present invention, it is possible to obtain a coating film that is less likely to become cloudy during the coating process and has excellent in-plane film thickness uniformity, and it is also possible to obtain a cured relief pattern that has excellent chemical resistance. The present invention is suitable for use in the field of photosensitive materials that are useful in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (14)

100 parts by weight of a polyimide precursor and/or a polyimide;
20 to 150 parts by mass of a radical polymerizable compound;
0.001 to 1 parts by weight of a surfactant;
0.1 to 10 parts by mass of a photopolymerization initiator;
A negative photosensitive resin composition comprising:
the surfactant is at least one selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant,
the radical polymerizable compound includes a nitrogen atom-containing radical polymerizable compound and a nitrogen atom-free radical polymerizable compound,
The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (1):
In formula (1), _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.
The polyimide precursor has a structural unit represented by
In the general formula (1), at least one of R ₁ and R ₂ is represented by the following general formula (2):
{In formula (2), L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}
and having a structural unit represented by
the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member,
The negative photosensitive resin composition, wherein the nitrogen atom-containing radical polymerizable compound has a urea group . The negative-type photosensitive resin composition according to claim 1, wherein the negative-type photosensitive resin composition contains the polyimide precursor but does not contain the polyimide. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the surfactant is a fluorine-containing surfactant. The negative photosensitive resin composition according to any one of claims 1 to 3 , wherein the nitrogen atom-containing radical polymerizable compound further has a hydroxyl group . The negative-type photosensitive resin composition according to any one of claims 1 to 4, wherein the radically polymerizable compound comprises a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound. The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (3):
{In formula (3), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
The negative photosensitive resin composition according to any one of claims 1 to 5, comprising a polyimide precursor having a structural unit represented by the formula: The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (4):
{In formula (4), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
The negative photosensitive resin composition according to any one of claims 1 to 6, comprising a polyimide precursor having a structural unit represented by the following formula: The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (5):
{In formula (5), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
The negative photosensitive resin composition according to any one of claims 1 to 7, comprising a polyimide precursor having a structural unit represented by the formula: The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6):
{In formula (6), _n1 is an integer of 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.}
The negative photosensitive resin composition according to any one of claims 1 to 8, comprising a polyimide precursor having a structural unit represented by the formula: The negative-type photosensitive resin composition according to any one of claims 1 to 9, wherein the insulating member is an interlayer insulating film. (1) applying the negative photosensitive resin composition according to any one of claims 1 to 10 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of: heat-treating the relief pattern to form a cured relief pattern. The method for producing a cured relief pattern according to claim 11, wherein the heat treatment in step (4) is a heat treatment at 200°C or less. The method for producing a cured relief pattern according to claim 11, wherein the heat treatment in step (4) is a heat treatment at 170°C or less. A method for producing polyimide, comprising curing the negative-type photosensitive resin composition described in any one of claims 1 to 10.