JP7209809B2 - Alkali-soluble polyimide, method for producing same, negative photosensitive resin composition, cured film, and method for producing patterned cured film - Google Patents

Description

TECHNICAL FIELD The present invention relates to an alkali-soluble polyimide, a method for producing the same, a negative photosensitive resin composition containing the polyimide, and a cured film comprising a cured product thereof.

Photosensitive resins that can be easily patterned by photolithography are widely used in the field of electronics such as semiconductors and displays. A photosensitive resin composition containing a polyimide resin imparted with alkali solubility by introducing an acidic group has excellent heat resistance.

A phenolic hydroxyl group and a carboxy group are mentioned as an acidic group introduced in order to provide alkali solubility. For example, Patent Document 1 describes a negative photosensitive resin composition containing an alkali-soluble polyimide resin into which a carboxyl group is introduced as an acidic group.

JP-A-2000-34347

Since phenolic hydroxyl groups have low acidity (high pKa), it is necessary to increase the amount of phenolic hydroxyl groups introduced in order to make the polyimide soluble in an alkaline developer, which can cause a decrease in transparency. . Polyimides to which alkali-solubility has been imparted by introducing carboxyl groups tend to be poor in heat resistance because the carboxy groups are easily oxidized or thermally decomposed when heated to high temperatures.

In view of the above, an object of the present invention is to provide a polyimide having excellent heat resistance while maintaining alkali solubility, and a photosensitive resin composition containing the polyimide.

The present inventors have found that a polyimide having an NH group in which a hydrogen atom is bonded to a nitrogen atom in the isocyanuric acid skeleton as a soluble group (acidic group) in an alkaline developer has excellent heat resistance and electrical insulation. The inventors have also found that they are excellent, and have completed the present invention.

A polyimide according to one embodiment of the present invention has an NH group that is an acidic group derived from an isocyanuric acid skeleton. A polyimide containing an NH group in an isocyanuric acid skeleton has a structure represented by the following general formula (1) and/or a structure represented by general formula (2).

Z in general formula (2) is hydrogen or a monovalent organic group. X in general formulas (1) and (2) includes a structure represented by general formula (3) below.

R ¹ in general formula (3) is a divalent organic group, R ² is a tetravalent organic group, and m is an integer of 1 or more.

In the above polyimide, the content of NH groups in which hydrogen atoms are bonded to nitrogen atoms in the isocyanuric acid skeleton is preferably 0.01 to 10 mmol/g.

In the above polyimide, R ¹ in general formula (3) may be one or more selected from the group consisting of a polysiloxane structure, an alicyclic structure, and a perfluoroalkyl group, and general formula (3) may be one or ^more selected from the group consisting of an alicyclic structure and a perfluoroalkyl group.

An example of the structure X in the above general formula (1) is a structure represented by the following general formula (3a).

The isocyanuric acid skeleton-containing polyimide containing the structure represented by the general formula (3a) is, for example, a maleimide-terminated polyimide prepolymer represented by the following general formula (5) and an isocyanuric acid represented by the following general formula (III) It can be prepared by an addition reaction with a compound.

Other specific examples of the structure X in the general formula (1) include structures represented by the following general formula (3b).

Y in general formula (3b) is a direct bond or a divalent organic group. As a specific example in which Y is a divalent organic group, the polyimide may contain a structure represented by the following general formula (3c). As a specific example in which Y is a direct bond, the polyimide may contain a structure represented by the following general formula (3d).

^In general formulas (3b) , (3c) and (3d) , R4 and R6 are ^each independently hydrogen, halogen or a monovalent organic group. The carbon number of the organic group is, for example, in the range of 1-20.

The isocyanuric acid skeleton-containing polyimide containing the structure represented by the general formula (3b) is obtained, for example, by reacting an isocyanuric acid skeleton-containing diamine represented by the general formula (8) with a tetracarboxylic dianhydride to obtain polyamic acid. can be prepared by synthesizing and imidizing polyamic acid by cyclodehydration.

One embodiment of the present invention is a negative photosensitive resin composition containing the above alkali-soluble polyimide, containing (A) the above polyimide, (B) a photopolymerizable compound, and (C) a photopolymerization initiator do. The negative photosensitive resin composition may further contain (D) a photosensitizer.

One embodiment of the present invention is a cured film comprising a cured product of the above negative photosensitive resin composition. The cured film may be patterned. For example, a patterned cured film can be formed by applying the above negative type photosensitive resin composition in a layer, performing photocuring by pattern exposure, and dissolving and removing the resin composition in the unexposed areas by alkali development.

The negative photosensitive resin composition containing the above polyimide has excellent patterning properties, and also has excellent heat resistance and electrical insulation.

[Polyimide]
One embodiment of the present invention is a polyimide with specific alkali-soluble groups. Polyimide is a polymer having an imide bond and is known as one of polymers with high heat resistance. Polyimide is generally obtained by polymerizing polyamic acid by reacting a diamine and a tetracarboxylic dianhydride, and then dehydrating and cyclizing (imidizing) the polyamic acid. A polyimide can also be obtained directly by reacting a diisocyanate compound with a tetracarboxylic dianhydride.

The polyimide of this embodiment has an NH group of an isocyanuric acid skeleton. Since the NH group of the isocyanuric acid skeleton is an acidic group, polyimide exhibits alkali solubility.

A polyimide having an NH group in an isocyanuric acid skeleton has a structure represented by the following general formulas (1) and/or (2).

In general formula (2), Z is hydrogen or a monovalent organic group. Examples of monovalent organic group Z include reactive groups such as alkyl groups such as methyl groups, aryl groups such as phenyl groups and benzyl groups, allyl groups and glycidyl groups.

In general formulas (1) and (2), X includes a repeating unit (polyimide chain) represented by general formula (3).

In general formula (3), R ¹ is a divalent organic group, R ² is a tetravalent organic group, and m is an integer of 1 or more. R ¹ is a diamine residue, which is an organic group obtained by removing two amino groups from the diamine represented by the general formula (I) below. When polyimide is synthesized using diisocyanate, ^R1 is a diisocyanate residue, which is an organic group obtained by removing two isocyanate groups from a diisocyanate compound. R ² is a tetracarboxylic dianhydride residue, which is an organic group obtained by removing two carboxyl anhydride groups from the tetracarboxylic dianhydride represented by the following general formula (II).

Examples of tetracarboxylic dianhydrides used for preparing polyimides, that is, compounds represented by the general formula (II) include pyromellitic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Aromatic tetracarboxylic dianhydrides in which four carbonyls are bonded to one aromatic ring such as dianhydrides, 2,3,6,7-naphthalenetetracarboxylic dianhydrides; 2,2-bis[4 -(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3,4,4-tetracarboxylic dianhydride, 3,3 ,4,4-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3 , 4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride and the like have two carbonyl groups on different aromatic rings. Bound aromatic tetracarboxylic dianhydride; 4,4′-hexafluoropropylidene diphthalic dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoro fluoroalkyl group-containing aromatic acid dianhydrides such as propane dianhydride; chain aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxy Cyclopentylacetic dianhydride, 3,5,6-tricarboxynorbonane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran l)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydrides such as

Examples of diamines used for preparing polyimides, that is, compounds represented by the above general formula (I) include [bis(4-amino-3-carboxy)phenyl]methane, p-phenylenediamine, and m-phenylenediamine. , 4,4′-diaminodiphenylmethane, 4,4′-diaminophenylethane, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1-(4′-amino phenyl)-1,3,3-trimethylindane, 6-amino-1-(4′-aminophenyl)-1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,4′-diamino Diphenyl ether, 2,7-diaminofluorene, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetra chloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-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-phenylenediisopropylidene)bisaniline, 4,4 '-(m-phenylenediisopropylidene)bisaniline, 4,4'-diaminophenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4' -aromatic diamines such as diaminodiphenyl sulfide and diaminotetraphenylthiophene; 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 2,2-bis (4-aminophenyl)hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-amino phenoxy)phenyl]hexafluoropropane, 2,2′-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4′-bis[4-(4-amino-2 fluoroalkyl group-containing aromatic diamines such as -trifluoromethyl)phenoxy]-octafluorobiphenyl; Chain aliphatic diamines such as methylenediamine and 4,4-diaminoheptamethylenediamine; 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4′-bis(aminocyclohexyl)methane, 3 ,3′-bis(aminocyclohexyl)methane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanidimethylenediamine, tricyclo[6,2,1,02.7]-undecylene Alicyclic diamines such as dimethyldiamine and 4,4'-methylenebis(cyclohexylamine) can be mentioned.

A silicone diamine having a polysiloxane structure represented by the following general formula (4) can also be used as the diamine.

In general formula (4), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a vinyl group, and n is an integer of 1 or more. The number n of repeating units in the organosiloxane structure is preferably 100 or less. n is, for example, 1-50.

Specific examples of silicone diamines include bis(4-aminophenyl)tetramethylsiloxane, bis(4-aminophenyl)tetramethyldisiloxane, bis(γ-aminopropyl)tetramethyldisiloxane, 1,4-bis(γ -aminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, bis(γ-aminopropyl)tetraphenyldisiloxane, amino-modified dimethylsilicone at both ends (for example, commercially available products manufactured by Shin-Etsu Chemical Co., Ltd. " X22-161A", "X22-161B", "KF-8010", "KF-8012" and "KF-8008"; Dow "BY16-835U"; and Chisso "Silaplane FM-3321"), both Terminal amino-modified methylphenyl silicones (for example, commercially available products are "X22-1660B-3" and "X22-9409" manufactured by Shin-Etsu Chemical Co., Ltd.).

In general formula (3), when m is 2 or more, multiple types of R ¹ and R ² may be included. For example, by using two or more diamines, a polyimide containing multiple types of ^R1 can be obtained, and by using two or more tetracarboxylic dianhydrides, a polyimide containing multiple types of ^R2 can be obtained. .

<Method for preparing polyimide having an isocyanuric acid skeleton>
There is no particular limitation on the method for producing the polyimide containing the structures represented by the general formulas (1) and/or (2).

(Preparation of polyimide by addition reaction of terminal-modified prepolymer and isocyanuric acid)
A polyimide having an NH group in which a hydrogen atom is bonded to the nitrogen atom of the isocyanuric acid skeleton is synthesized, for example, by synthesizing a polyimide or polyamic acid (terminal-modified prepolymer) having a specific reactive group at the terminal, and reacting the terminal of the prepolymer. obtained by a method of reacting a functional group with an isocyanuric acid or an isocyanuric acid derivative represented by general formula (III).

Z in general formula (III) is hydrogen or a monovalent organic group.

An example of a prepolymer having a reactive group at its terminal is a maleimide-terminated polyimide represented by the following general formula (5). R ¹ , R ² and m in general formula (5) are the same as R ¹ , R ² and m in general formula (3).

A maleimide-terminated polyimide may be prepared according to a conventional method. For example, a maleimide-terminated polyimide can be obtained by reacting a diamine with a tetracarboxylic dianhydride and maleic anhydride to synthesize a polyamic acid having a maleic acid monoamide at the end, followed by imidization by cyclodehydration. An amine-terminated polyamic acid is synthesized by reacting a tetracarboxylic dianhydride with an excess amount of diamine (for example, 1.001 to 1.1 times in molar ratio) relative to the tetracarboxylic dianhydride, and the terminal may be reacted with maleic anhydride to synthesize a polyamic acid having a terminal maleic acid monoamide.

As diamines and tetracarboxylic dianhydrides, for example, the diamines and tetracarboxylic dianhydrides exemplified above are used. An isocyanuric acid skeleton-containing diamine described later may be used as part of the diamine.

Maleimide-terminated polyimides as prepolymers preferably exhibit solvent solubility. For example, by using a tetracarboxylic dianhydride and/or a diamine having an alicyclic structure or a perfluoroalkyl group, a solvent-soluble polyimide can be obtained.

When the maleimide-terminated polyimide is reacted with isocyanuric acid, a polyimide having a structural unit represented by the following general formula (6) is formed by the Michael addition reaction between the terminal maleimide group of the polyimide chain and the NH group of the isocyanuric acid skeleton. can get.

A polyimide having a structural unit represented by the general formula (6) corresponds to a polyimide in which the organic group X in the general formulas (1) and (2) is represented by the following general formula (3a).

The polyimide obtained by reacting the maleimide-terminated polyimide with isocyanuric acid may have a structure represented by the following general formula (7) at the terminal.

A polyimide having a structural unit represented by general formula (7) corresponds to the case where Z in general formula (2) above is hydrogen.

By using an isocyanuric acid derivative in which Z in the general formula (III) is a monovalent organic group instead of or in addition to isocyanuric acid, Z in the general formula (2) is an organic group A polyimide having a terminal structure is obtained.

An isocyanuric acid derivative in which Z is an organic group in general formula (III) is a monosubstituted isocyanurate in which a hydrogen atom bonded to one of the three nitrogen atoms of isocyanuric acid is substituted with an organic group Z. Mono-substituted isocyanurates include monomethyl isocyanurate, monoallyl isocyanurate, monoglycidyl isocyanurate, monobenzyl isocyanurate and the like.

In the general formula (5) above, a bismaleimide-substituted polyimide having maleimide groups at both ends is shown as the maleimide-terminated polyimide. good. Also, the maleimide-terminated polyimide may be a mixture of a polyimide having maleimide groups at both ends and a polyimide having a maleimide group at only one end.

In the preparation of polyimides having an isocyanuric acid backbone, other compounds may be used in addition to the maleimide-terminated polyimides and isocyanuric acid and/or isocyanuric acid derivatives. For example, a maleimide compound that does not contain a polyimide chain may be used for the purpose of adjusting the content of the isocyanuric acid skeleton (NH group, which is an acidic group) and the molecular weight of the polyimide.

Examples of maleimide compounds containing no polyimide chain include N,N'-ethylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-1,4-phenylenebis Maleimide, N,N'-1,3-phenylenebismaleimide, 4,4'-methylenebis(N-phenylmaleimide), bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,2-bis Examples include bismaleimides such as [4-(4-maleimidophenoxy)phenyl]propane and bis(2-maleimidoethyl)disulfide.

These bismaleimides have shorter chain lengths and lower molecular weights than polyimides. Therefore, the use of bismaleimide in addition to maleimide-terminated polyimide tends to reduce the average chain length between isocyanuric acid skeletons in the polymer chain and increase the content of NH groups per unit mass. On the other hand, by using a polyfunctional amine such as diamine, it is possible to reduce the content of NH groups in the isocyanuric acid skeleton in the polymer.

Monomaleimides such as maleimide, N-alkylmaleimide, and N-phenylmaleimide may be used as the maleimide compound containing no polyimide chain. In addition to isocyanuric acid and/or monosubstituted isocyanurates, amines and bissubstituted isocyanurates may also be used. Monomaleimides, monoamines, bis-substituted isocyanurates, etc. are monofunctional compounds having only one reaction point in one molecule in the addition reaction of maleimide and amine. Molecular weight can be adjusted.

(Preparation of polyimide using a monomer having an isocyanuric acid skeleton)
A polyimide having an NH group in which a hydrogen atom is bonded to a nitrogen atom of an isocyanuric acid skeleton can also be obtained by a method using an isocyanuric acid derivative as a tetracarboxylic dianhydride and/or a diamine or a diisocyanate as a raw material (monomer) of the polyimide. be done. Among them, a method of using a diamine having an isocyanuric acid skeleton or a diisocyanate having an isocyanuric acid skeleton is convenient.

Isocyanuric acid skeleton-containing diamines and isocyanuric acid skeleton-containing diisocyanates can be obtained by various methods. For example, an isocyanuric acid skeleton-containing diamine represented by the following general formula (IV) can be prepared by reacting isocyanuric acid with a nitroalkyl halide in a molar ratio of 1:2 to reduce the nitro group for amination; It can be obtained by a method of reacting an isocyanate compound with potassium cyanate at a molar ratio of 2:1, reducing the nitro group and aminating it. An isocyanuric acid skeleton-containing diisocyanate represented by the following general formula (V) is obtained by reacting a diisocyanate compound with potassium cyanate at a molar ratio of 2:1.

In general formulas (IV) and (V) ^, R3 is a divalent organic group.

An example of the diamine represented by the general formula (IV) is a diamine compound represented by the following general formula (8).

In general formula (8), Y is a direct bond or a divalent organic group, and ^R4 is hydrogen, halogen or a monovalent organic group. Examples of monovalent organic groups include organic groups having 1 to 20 carbon atoms.

A polyimide obtained by reacting a diamine compound represented by the general formula (8) with a tetracarboxylic dianhydride represented by the general formula (II) to cyclodehydrate the polyamic acid is the following general A structural unit represented by formula (9) is included.

A polyimide having a structural unit represented by the general formula (9) corresponds to a polyimide in which the organic group X in the general formula (1) is represented by the following general formula (3b).

An example of the diamine compound represented by the general formula (8) is a diamine compound in which Y is a direct bond. A diamine compound in which Y is a direct bond is represented by the following general formula (10).

The diamine compound of the general formula (10) can be obtained, for example, by reacting a nitrophenyl isocyanate represented by the following general formula (VI) with potassium cyanate at a molar ratio of 2:1 to obtain a bis(nitrophenyl)-substituted isocyanurate. It is obtained by synthesis, reduction of the nitro group and amination.

^R4 is hydrogen, halogen or a monovalent organic group. Examples of monovalent organic groups include organic groups having 1 to 20 carbon atoms. R ⁴ is preferably hydrogen or a methyl group. Specific examples of the nitrophenyl isocyanate of general formula (VI) include the following compounds.

A diamine compound in which Y is a divalent organic group in the general formula (8) can be obtained, for example, by a coupling reaction between a bis(halogenated phenyl)-substituted isocyanurate and a compound containing —Y—NH ₂ . A bis(halogenated phenyl)-substituted isocyanurate can be obtained by reacting a halogen-substituted phenyl isocyanate represented by the following formula with potassium cyanate in a molar ratio of 2:1.

^R6 is hydrogen, halogen or a monovalent organic group. Examples of monovalent organic groups include organic groups having 1 to 20 carbon atoms.

An example of the diamine compound in which Y in the general formula (8) is a divalent organic group is a compound represented by the following general formula (11).

^R4 and ^R6 are each independently hydrogen, halogen, or an organic group.

The compound represented by the general formula (11) is a cross-coupling (Sonogashira coupling) reaction between a bis(halogenated phenyl)-substituted isocyanurate and an ethynylaniline which may have a substituent on the benzene ring. can be synthesized by

A polyimide obtained by reacting a diamine represented by the general formula (11) with a tetracarboxylic dianhydride and cyclodehydrating the polyamic acid has the following general formula ( 3c) corresponds to polyimide. A polyimide containing a diamine-derived structure represented by the general formula (11) has high heat resistance.

<Composition of polyimide>
As described above, since the NH group in the isocyanuric acid skeleton is an acidic group, the polyimide having the NH group in the isocyanuric acid skeleton exhibits alkali solubility. The higher the content of NH groups in the isocyanuric acid skeleton, the higher the alkali solubility. The amount of NH groups in the isocyanuric acid skeleton contained in the polyimide may be set according to the type of alkaline developer and development conditions. The amount of NH groups in the isocyanuric acid skeleton contained in the polyimide is, for example, 0.01 to 10 mmol/ g . It may be 3-4 mmol/g, or 0.5-3.5 mmol/g.

When introducing an isocyanuric acid skeleton by reacting a terminal-modified polyimide (or polyamic acid) with a prepolymer with isocyanuric acid and/or an isocyanuric acid derivative, adjustment of the molecular weight (chain length) of the prepolymer or By using a reactive compound (eg, bismaleimides) in combination, the amount of NH groups in the polyimide can be adjusted within a desired range. When using a diamine having an isocyanuric acid skeleton as a polyimide raw material monomer, the ratio of the diamine having an isocyanuric acid skeleton and other diamines is adjusted to adjust the amount of NH groups in the polyimide to the desired range. can.

In order to form a layered resin composition containing a polyimide resin, the polyimide preferably exhibits solubility in an organic solvent. When used for optical applications such as displays, polyimide preferably has little coloration and high transparency. The properties of these polyimides depend on the structure of the polyimide chain in addition to the NH group content of the isocyanuric acid skeleton.

For example, when the polyimide chain contains an alicyclic structure or a perfluoro group, the solubility and transparency of the polyimide tend to improve. Moreover, when the polyimide chain has a polysiloxane structure, the transparency of the polyimide tends to be improved. By using diamines and/or tetracarboxylic dianhydrides having these structures, polyimides containing alicyclic structures, polysiloxane structures, and/or perfluoro groups can be obtained.

Specifically, a diamine containing a polysiloxane structure, an alicyclic structure, and/or a perfluoroalkyl group is used as the divalent organic group R ¹ in general formula (I), and 4 in general formula (II) As functional organic radicals R ² , preference is given to using tetracarboxylic dianhydrides containing cycloaliphatic structures and/or perfluoroalkyl groups. As diamines and tetracarboxylic dianhydrides containing perfluoroalkyl groups, those in which perfluoro groups are bonded to one or more of the carbon atoms constituting an aromatic ring are preferred.

[Negative photosensitive resin composition]
Said polyimide can be used for various uses. Since the polyimide having an NH group in the isocyanuric acid skeleton exhibits alkali solubility, a resin composition containing a photocurable compound can be used as an alkali-soluble photosensitive resin composition.

One embodiment of the present invention is a negative photosensitive resin composition containing (A) the above polyimide as a binder resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. be. The negative photosensitive resin composition may further contain (D) a photosensitizer.

<(B) Photopolymerizable compound>
The photopolymerizable compound has at least one photopolymerizable functional group in one molecule. The photopolymerizable compound preferably has two or more photopolymerizable functional groups in one molecule, and may have three or more photopolymerizable functional groups in one molecule. If the photopolymerizable compound is polyfunctional, the photoreactivity is enhanced, the crosslink density of the cured film is increased, and a film having excellent mechanical strength can be easily obtained.

A photopolymerizable functional group means a functional group that polymerizes and crosslinks with a radical species or an acid (cationic species) generated from a photopolymerization initiator when externally irradiated with an active energy ray. Active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays and i-rays.

The reaction mode and cross-linking mode of the photopolymerizable functional group are not particularly limited. From the viewpoint of reactivity, photopolymerizable compounds include (meth)acrylate compounds having a (meth)acryloyl group, epoxy compounds having an epoxy group, oxetane compounds having an oxetanyl group, alkoxysilane compounds having an alkoxysilyl group, and maleimide. A maleimide compound having a group, a vinyl ether compound having a vinyloxy group, and the like are preferable. Among these, (meth)acrylate compounds are preferred because of their high photoreactivity (photosensitivity).

Specific examples of (meth)acrylate compounds include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and modified allyl (meth)acrylate. Glycidyl ether (e.g. "Denacol Acrylate DA111" manufactured by Nagase ChemteX), urethane (meth)acrylates, epoxy (meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylol propane tetra (meth) acrylate, dipentaerythritol hexa(meth)acrylate, butanediol di(meth)acrylate, nonanediol di(meth)acrylate, polyalkylene glycol-based (meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate and (meth)acrylate group-containing polyorganosiloxane.

From the viewpoint of stability, the epoxy group of the epoxy compound is preferably an alicyclic epoxy group or a glycidyl group. Among them, an alicyclic epoxy group is preferable because of its excellent cationic photopolymerizability.

Specific examples of epoxy compounds include novolak phenol-type epoxy resins, biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, cyclohexyl epoxy group-containing polyorganosiloxanes, glycidyl group-containing polyorganosiloxanes, bisphenol F diglycidyl ether, and bisphenol A diglycidyl. ether, 2,2′-bis(4-glycidyloxycyclohexyl)propane, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4- epoxycyclohexyl)adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate and diallyl monoglycidyl isocyanurate. The polyorganosiloxane in the cyclohexyl epoxy group-containing polyorganosiloxane and the glycidyl group-containing polyorganosiloxane may be linear or cyclic.

Specific examples of the oxetane compound include 1,4-bis{(3-ethyl-3-oxetanyl)methoxy}methyl}benzene, bis{1-ethyl(3-oxetanyl)}methyl ether, 3-ethyl-3-( phenoxymethyl)oxetane and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

As the alkoxysilyl group of the alkoxysilane compound, the functional group bonded to silicon is a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group or tert-butoxy group. is mentioned. The functional group that bonds to silicon is preferably a methoxy group or an ethoxy group because it can suppress the remaining of residual components after curing.

Specific examples of alkoxysilane compounds include tris[3-(trimethoxysilyl)propyl] isocyanurate, tetramethoxy(ethoxy)silane and its condensates, methyltrimethoxy(ethoxy)silane and its condensates, and dimethyldimethoxy ( ethoxy)silanes and condensates thereof.

<(C) Photoinitiator>
The type of photopolymerization initiator is not particularly limited, and may be appropriately selected from photocationic polymerization initiators, photoradical polymerization initiators, and the like according to the type of photopolymerizable compound.

Examples of photocationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds, bis( perfluoroalkylsulfonyl )methane metal salts, aryl diazonium compounds, aromatic onium salts of Group VIa elements, and aromatic compounds of Group Va elements. Onium salts, dicarbonyl chelates of group IIIa-Va elements, thiopyrylium salts, MF ₆ ^-anions (M is phosphorus, antimony or arsenic), arylsulfonium complex salts, aromatic iodonium complex salts and aromatic sulfonium complex salts, [4-(diphenyl sulfonio)phenyl]sulfide-bishexafluoro metal salts (e.g. phosphates, arsenates, antimonates, etc.), aromatic iodonium complexes and aromatic sulfoniums where the anion is B(C ₆ F ₅ ) ₄ ^— complex salts and the like.

Examples of photoradical polymerization initiators include acetophenone compounds, benzophenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, biimidazole compounds, α-diketone compounds, titanocene compounds, and polynuclear quinone compounds. , xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds and fluoroamine compounds. . Acetophenone-based compounds are preferable as the radical photopolymerization initiator from the viewpoint of availability and the like.

<(D) Photosensitizer>
The negative photosensitive resin composition may contain a photosensitizer. Addition of a photosensitizer can impart sensitivity to visible light such as g-line (436 nm), h-line (405 nm) and i-line (365 nm) and long wavelength ultraviolet light (UVA). The curing reactivity of the negative photosensitive resin composition can be adjusted by using the above-described photopolymerization initiator and sensitizer together. Examples of sensitizers include anthracene-based compounds and thioxanthone-based compounds.

Specific examples of anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di- and tert-butylanthracene. Among them, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene and 9,10-diethoxyanthracene are preferred.

Specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone and 2,5- diethylthioxanthone .

<Solvent>
The negative photosensitive resin composition is preferably used as a solution in which each of the above components is dissolved in a solvent. The solvent is not particularly limited as long as it can dissolve each of the above components, hydrocarbon solvents such as benzene, toluene, hexane and heptane; tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether. Ether solvents; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and ethylene glycol diethyl ether; Chloroform, methylene chloride and 1 , 2-dichloroethane and other halogen-based solvents.

<Other ingredients>
In addition to the components (A), (B), (C), and (D) and the solvent, the negative photosensitive resin composition may contain various additives within a range that does not impair the object and effect of the present invention. good. Additives include silane coupling agents, ultraviolet absorbers, colorants, release agents, flame retardants, flame retardant aids, surfactants, defoaming agents, emulsifiers, leveling agents, anti-repellent agents, ion trapping agents ( antimony-bismuth, etc.), thixotropic agents, tackifiers, storage stability improvers, antiozonants, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, heat stabilizers , conductivity imparting agents, antistatic agents, radiation shielding agents, nucleating agents, phosphorus peroxide decomposers, lubricants, pigments, metal deactivators, thermal conductivity imparting agents and physical property modifiers.

<Formulation of negative photosensitive resin composition>
The negative photosensitive resin composition may contain other resins as (A) binder resin in addition to the polyimide resin described above. (B) The photopolymerizable compound, (C) the photopolymerization initiator, and (D) the photosensitizer may be used in combination of two or more.

The content of (A) the binder resin in the negative photosensitive resin composition is preferably 20 to 98 parts by weight, more preferably 30 to 95 parts by weight, and 50 to 93 parts by weight with respect to 100 parts by weight of the total solid. More preferred. The content of the binder resin relative to the total solid content may be 60 parts by weight or more, 65 parts by weight or more, or 70 parts by weight or more, and may be 90 parts by weight or less, or 85 parts by weight or less.

From the viewpoint of ensuring heat resistance and alkali solubility, the amount of the above polyimide resin with respect to the total amount of 100 parts by weight of the binder resin is preferably 50 parts by weight or more, preferably 70 parts by weight or more, 80 parts by weight or more, and 90 parts by weight. Above, it may be 95 parts by weight or more, 99 parts by weight or more, or 100 parts by weight.

The content of the photopolymerizable compound (B) in the negative photosensitive resin composition is preferably 2 to 80 parts by weight, more preferably 5 to 70 parts by weight, and 7 to 50 parts by weight, based on 100 parts by weight of the total solid. Part is more preferred. The content of the photopolymerizable compound relative to the total solid content may be 10 parts by weight or more, 12 parts by weight or more, 15 parts by weight or more, 18 parts by weight or more, or 20 parts by weight or more, 40 parts by weight or less, or 35 parts by weight. parts or less or 30 parts by weight or less.

(C) The amount of the photopolymerization initiator is, for example, 0.1 to 80 parts by weight, preferably 1 to 50 parts by weight, and 3 to 40 parts by weight with respect to 100 parts by weight of the photopolymerizable compound (B). is more preferred. When the amount of the polymerization initiator is small, the curing tends to be insufficient, and the contrast of the cured pattern film after alkali development tends to decrease. If the amount of the polymerization initiator is excessively large, the cured film may be colored and the transparency may be lowered.

The amount of the sensitizer (D) is preferably 0.01 to 300 mol, more preferably 0.1 to 100 mol, per 1 mol of the photopolymerization initiator. If the amount of sensitizer is too small, it may take a long time to cure and may adversely affect developability. On the other hand, if the amount of the sensitizer is excessively large, the film may be colored due to residue, or the coating may be colored or deteriorated due to rapid curing.

<Formation of cured film>
A negative photosensitive resin composition containing an alkali-soluble polyimide can be used for various purposes, for example, it is used to form a patterned cured film using photolithography. Since polyimide as a binder resin is excellent in heat resistance and insulation, a cured film made of a cured product of a negative photosensitive resin composition can be applied as an insulating cured film in semiconductors, displays, electronic circuit boards, and the like.

By applying the negative photosensitive resin composition in layers on a substrate and drying the solvent, a laminate having a coating film of the photosensitive resin composition formed on the substrate can be obtained. Heating (pre-baking) may be performed for solvent removal. By subjecting the coating film of the laminate to pattern exposure through a pattern mask, the resin composition in the exposed portion is photocured. By performing development using an alkaline developer, the negative photosensitive resin composition in the unexposed areas is dissolved and removed to obtain a patterned cured film. After development, heating (post-baking) may be performed for the purpose of improving physical properties of the cured film. The thickness of the cured film is, for example, about 1 to 100 μm, and may be 10 μm or less or 5 μm or less.

The light source used for photocuring (exposure) may be selected according to the absorption wavelength of the polymerization initiator and sensitizer used, and includes a light source with a wavelength in the range of 200 to 450 nm (e.g., high pressure mercury lamp, ultra high pressure mercury lamps, metal halide lamps, high power metal halide lamps, xenon lamps, carbon arc lamps or light emitting diodes) can be used.

Although the exposure dose is not particularly limited, it is generally 1 to 10000 mJ/cm ² , preferably 5 to 3000 mJ/cm ² , more preferably 10 to 1000 mJ/cm ² . The exposure time is preferably 1 to 600 seconds, more preferably 1 to 150 seconds.

If the amount of exposure is too small, the negative photosensitive resin composition may not be cured. If the amount of exposure is large, the cured film may be discolored. The exposure dose may be 500 mJ/cm ² or less, 400 mJ/cm ² or less, or 300 mJ/cm ² or less. As described above, by using a photosensitizer and (B) using a compound with high photosensitivity such as (meth)acrylate as a photocurable compound, a patterned cured film with high contrast is formed even with a low exposure dose. It is possible.

After the exposure, the resin composition in the unexposed areas is dissolved and removed by developing by an immersion method, a spray method, or the like to obtain a cured film having a desired pattern. As the developer, a common alkaline developer can be used without particular limitation. Specific examples of the alkaline developer include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution; Inorganic alkali aqueous solution is mentioned. The developer may contain an alcohol, a surfactant, and the like for adjusting the dissolution rate and the like. The concentration (alkali concentration) of the developer is preferably 25% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less.

By using a low-concentration alkaline developer, the dissolution of the exposed portion is suppressed, and the contrast of the pattern cured film tends to be improved. As described above, by adjusting the content of the NH group (alkali-soluble group) of the isocyanuric acid skeleton in the polyimide, the resin composition exhibits excellent solubility even in a low-concentration alkaline developer, and the contrast is improved. A highly cured film can be formed.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to the following examples.

[Synthesis of diamine compound]
<Synthesis of diamine compound 1>
A reactor was charged with 1 L of N,N-dimethylformamide (DMF) and 38 g of potassium cyanate and heated to 75°C. 224 g of 4-nitrophenyl isocyanate was added dropwise using a dropping funnel, and after the dropwise addition was completed, the mixture was stirred for 30 minutes to complete the reaction. DMF was removed under reduced pressure, 1 L of ethyl acetate and 3 L of water were added, concentrated hydrochloric acid was added to the aqueous layer, the deposited precipitate was collected, and recrystallization was performed with ethanol to obtain white crystals.

A 500 mL flask was charged with 23.9 g of the above white crystals, 1 g of Pd-supported carbon, and 200 mL of dimethylacetamide, and the atmosphere in the flask was changed to H ₂ atmosphere, and the mixture was stirred at 90° C. for 3 hours to react. The reaction mixture was neutralized by adding an aqueous sodium hydrogencarbonate solution, and then filtered by adding ethyl acetate. Thereafter, the organic layer was washed with water, dried with magnesium sulfate, concentrated, purified with a silica column, and recrystallized with ethanol to obtain a diamine compound 1 represented by the following formula.

<Synthesis of diamine compound 2>
A diamine compound 2 represented by the following formula was obtained in the same manner as the synthesis of diamine compound 1 above, except that 2-methyl-4-nitrophenyl isocyanate was used instead of 4-nitrophenyl isocyanate.

<Synthesis of diamine compound 3>
A reaction vessel was charged with 1 L of DMF and 38 g of potassium cyanate and heated to 75°C. 4-Chlorophenyl isocyanate: 210 g was added dropwise with a dropping funnel, and after the dropwise addition was completed, the mixture was stirred for 30 minutes to complete the reaction. DMF was removed under reduced pressure, 1 L of ethyl acetate and 3 L of water were added, concentrated hydrochloric acid was added to the aqueous layer, the deposited precipitate was collected, and recrystallization was performed with ethanol to obtain white crystals.

A flask was charged with the above white crystals: 22.5 g, 4-ethynylaniline: 16.6 g, bis(triphenylphosphine)palladium(II) dichloride: 4.51 g, copper(I) iodide: 2.44 g, and triethylamine. : 500 mL was charged and stirred for 8 hours at 80°C under a nitrogen atmosphere to react. After completion of the reaction, triethylamine was removed under reduced pressure, and after purification with a silica column, recrystallization was performed with ethanol to obtain a diamine compound 3 represented by the following formula.

[Synthesis of cationic polymerizable polysiloxane compound]
Diallyl isocyanurate: 40 g and diallyl monomethyl isocyanurate: 29 g were dissolved in dioxane: 264 g, and a xylene solution of a platinum vinylsiloxane complex ("Pt-VTSC-3X" manufactured by Yumico Precious Metals Japan, platinum content: 3% by weight) was prepared. ): 143 μL added. This solution was prepared by dissolving 88 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane in 176 g of toluene under a nitrogen atmosphere containing 3% oxygen. It was added dropwise to the solution at 105° C. over 3 hours. After 30 minutes from the end of dropping, it was confirmed by ¹ H-NMR that the reaction rate of the alkenyl group was 95% or more.

A solution prepared by dissolving 62 g of 1-vinyl-3,4-epoxycyclohexane in 62 g of toluene was added dropwise to the above reaction solution over 1 hour. After 30 minutes from the end of dropping, it was confirmed by ¹ H-NMR that the reaction rate of the alkenyl group was 95% or more, and the reaction was terminated by cooling. After toluene and dioxane were distilled off under reduced pressure, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) was added to obtain a 75% by weight solution (colorless and transparent) of "modified siloxane B1" which is a cationic polymerizable compound.

[Preparation of polyimide resin]
In Synthesis Examples 1 to 3 below, a polyimide resin having an NH group in the isocyanuric acid skeleton was produced by performing an addition reaction with isocyanuric acid using a maleimide-terminated polyimide as a prepolymer. In Synthesis Examples 4 to 8, the diamine compounds synthesized above were used to prepare polyimide resins having an NH group in the isocyanuric acid skeleton.

<Synthesis Example 1>
In a flask, DMF: 18 g, 4,4'-hexafluoropropylidenediphthalic dianhydride (6FDA): 3.6 g, and 2,2'-bis(trifluoromethyl)benzidine (TFMB): 2.6 g was added and stirred at room temperature for 30 minutes under nitrogen atmosphere. Subsequently, after adding 0.80 g of maleic anhydride (MA), the mixture was stirred at room temperature under a nitrogen atmosphere for 120 minutes. Furthermore, DMF: 7.4 g, pyridine: 1.9 g, and acetic anhydride: 2.5 g were sequentially added to the flask and stirred for 3 hours while heating to 90°C. After cooling to room temperature, 500 mL of isopropyl alcohol was put into the flask and the precipitate was collected. Furthermore, it was washed three times with 500 mL of isopropyl alcohol, dried under reduced pressure at 80° C. for 6 hours, and produced maleimide-terminated polyimide a1 (prepared polyimide) having 5.5×10 ⁻² mmol/g of maleimide groups (measured by ¹ H-NMR). polymer) was obtained.

DMF: 20 g and isocyanuric acid: 2.5 g (19.4 mmol, amount of NH groups: 58.1 mmol) were put into a flask and stirred at 150°C under nitrogen. Maleimide-terminated polyimide a1: 4.2 g (amount of maleimide group: 0.231 mmol), and N,N-1,3-phenylenebismaleimide (1,3-PDM): 4.2 g (15.7 mmol, amount of maleimide group). Amount: 31.3 mmol) was dissolved in 20 g of DMF to prepare a solution. This solution was divided into 5 portions, added to the above isocyanuric acid solution, reacted at 150° C. for 8 hours, cooled to room temperature, and 500 mL of isopropyl alcohol was added to collect a precipitate. Further, after washing with isopropyl alcohol, it was dried under reduced pressure to obtain polyimide resin A1. Polyimide resin A1 contained 2.3 mmol/g of NH groups in the isocyanuric acid skeleton (measured by ¹ H-NMR).

<Synthesis Example 2>
In a flask, DMF: 18 g, 4,4'-oxydiphthalic dianhydride (ODPA): 2.5 g, 4,4'-diaminodiphenyl ether (ODA): 0.81 g, and siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd. "KF -8010"): 3.5 g was added and stirred for 30 minutes at room temperature under a nitrogen atmosphere. Then, in the same manner as in Synthesis Example 1, maleic anhydride was added and reacted, then DMF, pyridine, and acetic anhydride were sequentially added to react (imidation), followed by precipitation and washing with isopropyl alcohol. Drying was performed under reduced pressure to obtain a maleimide-terminated polyimide a2 (prepolymer) having 2.3×10 ⁻² mmol/g of maleimide groups.

Polyimide resin a2 and 1,3-PDM were prepared in the same manner as in Synthesis Example 1, except that polyimide a2: 5.5 g (maleimide group amount: 0.126 mmol) was used instead of polyimide a1: 4.2 g. and isocyanuric acid to obtain a polyimide resin A2 containing 2.4 mmol/g of NH groups in the isocyanuric acid skeleton.

<Synthesis Example 3>
DMF: 37 g, 1,3-bis(aminomethyl)cyclohexane (CBMA): 2.2 g, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA): 3.2 g were introduced into a flask. and stirred for 30 minutes at room temperature under a nitrogen atmosphere. Thereafter, in the same manner as in Synthesis Example 1, 1.6 g of maleic anhydride was added and reacted, and then 14 g of DMF, 3.8 g of pyridine, and 5.0 g of acetic anhydride were sequentially added to react (imide ), followed by precipitation with isopropyl alcohol, washing, and drying under reduced pressure to obtain a maleimide-terminated polyimide a3 (prepolymer) having 3.1×10 ⁻² mmol/g maleimide groups.

Polyimide resin a3 and 1,3-PDM were prepared in the same manner as in Synthesis Example 1, except that polyimide a3: 4.2 g (maleimide group amount: 0.130 mmol) was used instead of polyimide a1: 4.2 g. and isocyanuric acid to obtain a polyimide resin A3 containing 2.4 mmol/g of NH groups in the isocyanuric acid skeleton.

Table 1 shows a list of the charged amounts of the raw materials used in the production of the above polyimide resins A1 to A3. All numerical values in Table 1 and Table 2 below are masses (g).

<Synthesis Example 4>
DMF: 18 g, diamine compound 1: 2.5 g, and 6FDA: 3.6 g were put into a flask and stirred for 30 minutes at room temperature under a nitrogen atmosphere. After that, 7.4 g of DMF, 1.9 g of pyridine, and 2.5 g of acetic anhydride were successively added to the flask and stirred for 3 hours while being heated to 90°C. After cooling to room temperature, 500 mL of isopropyl alcohol was put into the flask and the precipitate was collected. Furthermore, it was washed three times with 500 mL of isopropyl alcohol and dried under reduced pressure at 80° C. for 6 hours to obtain polyimide resin A4.

<Synthesis Example 5>
Polyimide resin A5 was obtained in the same manner as in Synthesis Example 4, except that 2.5 g of diamine compound 2 was used instead of 2.5 g of diamine compound 1.

<Synthesis Example 6>
DMF: 18 g, diamine compound 1: 2.0 g, 4,4'-diaminodiphenyl ether (ODA): 0.5 g, and 6FDA: 4.5 g were added to a flask and stirred for 30 minutes at room temperature under a nitrogen atmosphere. . Thereafter, in the same manner as in Synthesis Example 4, polyimide resin A6 was obtained.

<Synthesis Example 7>
Polyimide resin A7 was obtained in the same manner as in Synthesis Example 4, except that 4.2 g of diamine compound 3 was used instead of 2.5 g of diamine compound 1.

<Synthesis Example 8>
DMF: 18 g, diamine compound 3 :4 . 2 g, siloxane diamine (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.): 1.5 g, CBDA: 1.5 g, and 6FDA: 3.6 g were added and stirred at room temperature for 30 minutes under a nitrogen atmosphere. Thereafter, in the same manner as in Synthesis Example 4, polyimide resin A8 was obtained.

Table 2 lists the charging amounts of the raw materials used to prepare the above polyimide resins A4 to A8.

[Preparation of photosensitive resin composition]
<Example 1>
Polyimide resin A1: 0.50 g as component (A), tris (2-acryloyloxyethyl) isocyanurate (manufactured by Hitachi Chemical "Fancryl FA-731A") as component (B): 0.10 g, component (C) Photoradical polymerization initiator ("Omnirad 184" manufactured by IGM RESINS): 0.025 g, and 9,10-dibutoxyanthracene (DBA) as a sensitizer: 0.025 g were dissolved in PGMEA as a solvent: 3.5 g. , a photosensitive resin composition 1 was prepared.

<Example 2>
A photosensitive resin composition 2 was prepared in the same manner as in Example 1, except that 0.50 g of polyimide resin A2 was used as component (A).

<Example 3>
A photosensitive resin composition 3 was prepared in the same manner as in Example 1, except that 0.50 g of polyimide resin A3 was used as component (A).

<Example 4>
Polyimide resin A1: 0.50 g as component (A), 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Celoxide 2021P" manufactured by Daicel) as component (B): 1.5 g, component As (C), a photocationic polymerization initiator (“CPI-210S” manufactured by San-Apro): 0.045 g and DBA 0.025 g as a sensitizer are dissolved in PGMEA 3.5 g as a solvent, and photosensitive resin composition 4 was prepared.

<Example 5>
Photosensitive resin composition 5 was prepared in the same manner as in Example 4, except that 0.50 g of modified siloxane B1 was used as component (B).

<Example 6>
A photosensitive resin composition 6 was prepared in the same manner as in Example 5, except that 0.50 g of polyimide resin A4 was used as component (A).

<Example 7>
Photosensitive resin composition 7 was prepared in the same manner as in Example 5, except that 0.50 g of polyimide resin A5 was used as component (A).

<Example 8>
A photosensitive resin composition 8 was prepared in the same manner as in Example 6, except that 0.50 g of polyimide resin A6 was used as component (A).

<Example 9>
A photosensitive resin was prepared in the same manner as in Example 7 except that 0.50 g of tris[3-(trimethoxysilyl)propyl] isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd. "KBE-9007N") was used as the component (B). Composition 9 was prepared.

<Example 10>
A photosensitive resin composition 10 was prepared in the same manner as in Example 7, except that 0.50 g of cyclohexyldivinyl ether was used as the component (B).

<Example 11>
Polyimide resin A5: 0.50 g as component (A), 4,4'-bismaleimide diphenylmethane: 0.10 g as component (B), photoradical polymerization initiator ("Omnirad 184" manufactured by IGM RESINS) as component (C): A photosensitive resin composition 11 was prepared by dissolving 0.025 g of DBA and 0.025 g of DBA as a sensitizer in 3.5 g of PGMEA as a solvent.

<Example 12>
A photosensitive resin composition 12 was prepared in the same manner as in Example 1, except that 0.50 g of polyimide resin A7 was used as component (A).

<Example 13>
A photosensitive resin composition 13 was prepared in the same manner as in Example 1, except that 0.50 g of polyimide resin A8 was used as component (A).

<Comparative Example 1>
As a comparison of component (A), a photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.50 g of a polyvinylphenol resin (Maruzen Petrochemical Co., Ltd. "Marukalinker M") was used instead of the polyimide resin. 14 was prepared.

[Formation and Evaluation of Insulating Film]
<Exposure sensitivity>
The resin compositions of Examples and Comparative Examples were spin-coated on a glass substrate so as to have a film thickness of 2 μm, and heated on a hot plate heated to 100° C. for 2 minutes. Next, an exposure apparatus (manufactured by Dainippon Kaken) equipped with a high-pressure mercury lamp is exposed through a photomask engraved with a line-and-space pattern of 50 μm in an integrated light amount range of 50 to 400 mJ/cm ² , and after 1 minute. It was immersed in an alkaline developer (TMAH 2.38% aqueous solution) for 180 seconds and washed with water for 30 seconds to form a pattern. Then, it was post-baked by heating on a hot plate at 230° C. for 30 minutes to prepare a patterning evaluation sample.

For each exposure amount sample, the pattern shape was observed using a 3D measurement laser microscope (Olympus "LEXT OLS4000" and a stylus type surface profiler (Veeco "Dektak150"), and film chipping occurred at 50 μm line and space. If the pattern is drawn without any defects, it is evaluated as OK.For each example and comparative example, the exposure amount required for the patterning evaluation to be OK was used as an index of exposure sensitivity.The smaller the exposure amount required for patterning, the lower the exposure sensitivity. , it can be said that the photosensitive resin composition has high sensitivity and is excellent.

<Heat resistance>
A cured film was produced in the same manner as described above, except that the exposure amount was 400 mJ/cm ² and the exposure was performed without passing through a photomask. Using the obtained cured film as a sample, a thermogravimetry device (TGA, manufactured by Shimadzu Corporation) was used to raise the temperature from room temperature to 500°C at a rate of 10°C/min, and the temperature (Td1) at which the weight decreased by 1% was determined. rice field.

<Electrical insulation>
A cured film was formed on the molybdenum thin film in the same manner as described above, except that a glass substrate with a molybdenum thin film was used, the exposure amount was 400 mJ/cm ² , and the exposure was performed without a photomask. An aluminum electrode (3 mmΦ) was formed on the cured film using a vacuum deposition machine, and a capacitor provided with the cured film between the molybdenum electrode and the aluminum electrode was produced. Using a semiconductor parameter analyzer (Agilent 4156), the volume resistivity of the cured film was calculated from the leakage current between the electrodes when a voltage of 30 V was applied.

<Evaluation results>
Compositions of photosensitive resin compositions of Examples 1 to 13 and Comparative Example 1 (types of components (A), (B), and (C)), and evaluation results (exposure sensitivity, 1% weight loss temperature Td1, and volume resistivity ) are shown in Table 3.

From the above results, the negative photosensitive resin composition containing a polyimide containing an NH group of an isocyanuric acid skeleton as a binder resin, when a radically polymerizable photopolymerizable compound is used as the component (B) (Example 1 to 3, 11 to 13) and the case of using a cationically polymerizable photopolymerizable compound (Examples 4 to 10), a negative photosensitive resin using a polymer having a phenolic hydroxyl group as the binder resin. It turns out that patterning by photolithography is possible similarly to the composition.

In addition, in Examples 1 to 13, compared with Comparative Example 1, the cured films have excellent heat resistance and insulating properties. In particular, the cured films of Examples 6 to 13 using polyimides A4 to A8 made from diamines (diamine compounds 1 to 3) having an isocyanuric acid skeleton have a 1% weight loss temperature Td1 of 350° C. or higher, The cured films of Examples 12 and 13 using the polyimides A7 and A8 made from the diamine compound 3 had a Td1 exceeding 400° C. and had excellent heat resistance.

On the other hand, the photosensitive resin composition using the polyimides A1 to A3 prepared by the addition reaction of the maleimide-terminated polyimide and isocyanuric acid, when a radically polymerizable photopolymerizable compound is used as the component (B) (Example 1 to 3) and the case of using a cationically polymerizable photopolymerizable compound (Examples 4 and 5), patterning is possible with a low exposure dose and the exposure sensitivity is excellent. In addition, from the comparison between Example 1 using polyimide A1 and Examples 4 and 5, it can be seen that a composition with high photosensitivity can be obtained by using a (meth)acryloyl group-containing compound as the component (B).

Claims (15)

A polyimide having a structure represented by the general formula (1) and/or a structure represented by the general formula (2):

Z in the general formula (2) is hydrogen or a monovalent organic group, and X in the general formulas (1) and (2) includes a structure represented by the following general formula (3),

R ¹ in general formula (3) is a divalent organic group containing one or more selected from the group consisting of a polysiloxane structure, an alicyclic structure, and a perfluoroalkyl group, and R ² is a tetravalent It is an organic group, and m is an integer of 1 or more. A polyimide having a structure represented by the general formula (1) and/or a structure represented by the general formula (2):

Z in the general formula (2) is hydrogen or a monovalent organic group, and X in the general formulas (1) and (2) includes a structure represented by the following general formula (3a),

R ¹ in general formula (3a) is a divalent organic group, R ² is a tetravalent organic group, and m is an integer of 1 or more. 3. The polyimide according to claim 2, wherein ^R1 in general formula (3a) contains one or more selected from the group consisting of a polysiloxane structure, an alicyclic structure, and a perfluoroalkyl group. Polyimide having a structure represented by general formula (1):

X in the general formula (1) includes a structure represented by the following general formula (3c),

R ² in general formula (3c) is a tetravalent organic group, and R ⁴ and R ⁶ are each independently hydrogen, halogen or a monovalent organic group. Claims 1 to 2, wherein R ² in the general formulas (3), (3a) and (3c 2 ) includes one or more selected from the group consisting of an alicyclic structure and a perfluoroalkyl group. 5. The polyimide according to any one of 4 . 6. The polyimide according to any one of claims 1 to 5 , wherein the content of NH groups in which hydrogen atoms are bonded to nitrogen atoms in the isocyanuric acid skeleton is 0.01 to 10 mmol/g. A method for producing a polyimide according to claim 2 or 3,
A method for producing a polyimide, in which an addition reaction is performed between a maleimide-terminated polyimide prepolymer represented by the general formula (5) and a compound represented by the general formula (III):

R ¹ in general formula (5) is a divalent organic group, R ² is a tetravalent organic group, m is an integer of 1 or more, and Z in general formula (III) is hydrogen or a monovalent is an organic group of A method for producing a polyimide according to claim 4,
Synthesizing a polyamic acid by reacting an isocyanuric acid skeleton-containing diamine represented by the general formula (11) with a tetracarboxylic dianhydride represented by the general formula (II),
A method for producing a polyimide, wherein the polyamic acid is imidized by cyclodehydration:

^R4 and R6 in general formula ( ¹¹ ) are each independently hydrogen, halogen or a monovalent organic group, and R2 in general formula ( ^II ) is a tetravalent organic group. A negative photosensitive resin composition comprising (A) the polyimide according to any one of claims 1 to 6 , (B) a photopolymerizable compound, and (C) a photopolymerization initiator. (A) a polyimide, (B) a photopolymerizable compound, and (C) a photopolymerization initiator,
A negative photosensitive resin composition in which the (A) polyimide has a structure represented by the general formula (1) and/or a structure represented by the general formula (2):

Z in the general formula (2) is hydrogen or a monovalent organic group, and X in the general formulas (1) and (2) includes a structure represented by the following general formula (3),

R ¹ in general formula (3) is a divalent organic group, R ² is a tetravalent organic group, and m is an integer of 1 or more. The (B) photopolymerizable compound is a (meth)acryloyl group-containing compound, an alicyclic epoxy group-containing compound, a glycidyl group-containing compound, an oxetanyl group-containing compound, an alkoxysilyl group-containing compound, a maleimide group-containing compound, and a vinyl ether group. The negative photosensitive resin composition according to claim 9 or 10 , comprising one or more compounds selected from the group consisting of containing compounds. The negative photosensitive resin composition according to any one of claims 9 to 11 , wherein the photopolymerizable compound (B) contains two or more photopolymerizable functional groups in one molecule. The negative photosensitive resin composition according to any one of claims 9 to 12 , further comprising (D) a photosensitizer. A cured film comprising a cured product of the negative photosensitive resin composition according to any one of claims 9 to 13 . The negative photosensitive resin composition according to any one of claims 9 to 13 is applied in a layer, the negative photosensitive resin composition is photocured by pattern exposure, and the unexposed area is subjected to alkali development. A method for producing a patterned cured film, comprising dissolving and removing a negative photosensitive resin composition.