JP5994235B2 - Photobase generator, photosensitive polyimide resin composition, method for producing relief pattern, and article - Google Patents

Description

  The present invention provides a photo-base generator for a precursor type photosensitive polyimide, a negative type photosensitive polyimide resin composition, a method for producing a relief pattern using the photosensitive polyimide resin composition, and the photosensitive polyimide resin composition. The present invention relates to an article manufactured using the same.

The photosensitive polyimide resin composition is used for, for example, electronic parts, optical products, molding materials for optical parts, layer forming materials or adhesives, and is particularly suitable for products or members formed through a patterning process using electromagnetic waves. It has been used.
Polyimide, which is a polymer material, exhibits top-class performance among organic materials, such as heat resistance, dimensional stability, and insulation characteristics, so it is widely applied to insulating materials for electronic components. Chip coating films in semiconductor devices In addition, it has been actively used as a base material for flexible printed wiring boards.

  In general, polyimide is poorly soluble in a solvent and difficult to process. As a method for patterning polyimide into a desired shape, patterning is performed by exposure and development in the state of a polyimide precursor having excellent solvent solubility, and then heat treatment. For example, there is a method of obtaining a polyimide pattern by imidization by the method described above.

Various methods have been proposed as means for forming a pattern using a polyimide precursor. Two typical ones are as follows.
(1) A method in which a polyimide precursor does not have a pattern forming ability and a pattern is formed by providing a photosensitive resin as a resist layer on the polyimide precursor.
(2) A method in which a photosensitive site is bonded or coordinated and introduced into the polyimide precursor itself, and a pattern is formed by its action. Alternatively, a method in which a photosensitive component is mixed with a polyimide precursor to form a resin composition, and a pattern is formed by the action of the photosensitive component.

  As a typical patterning technique using the above (2), (i) a polyimide precursor polyamic acid acts as a dissolution inhibitor before exposure to electromagnetic waves, and after exposure, a carboxylic acid is formed to form a dissolution accelerator; The naphthoquinonediazide derivative is mixed, and pattern formation is performed by increasing the contrast of the dissolution rate of the exposed area and unexposed area to the developer, followed by imidization to obtain a polyimide pattern (Patent Document 1) (Ii) A methacryloyl group is introduced into the polyimide precursor via an ester bond or an ionic bond, a photo radical generator is added thereto, and the exposed area is crosslinked to dissolve the exposed and unexposed areas in the developer. A method to obtain a polyimide pattern by forming a pattern by increasing the speed contrast and then imidizing it Etc. have been put into practical use (Patent Document 2).

  Compared with the method (1), the method (2) does not require a resist layer and can greatly simplify the process. However, in the method (i), a naphthoquinonediazide derivative is used to increase the solubility contrast. When the amount of addition is increased, there is a problem that the original physical properties of the polyimide cannot be obtained. Further, the method (ii) has a problem that the structure of the polyimide precursor is restricted.

  As another patterning technique, (iii) a polyamic acid that is a polyimide precursor is mixed with a photobase generator and heated after exposure to cause cyclization to proceed by the action of a base generated by exposure. A method for obtaining a polyimide pattern by forming a pattern by increasing the contrast of the dissolution rate with respect to the developer in the exposed area and the unexposed area by reducing the solubility in the film and then imidizing it has been reported. (Patent Document 3).

  Non-Patent Document 1 discloses the use of o-hydroxy-trans-cinnamic acid as a photoreactive protecting group for amines. Patent Document 4 discloses a photosensitive polyimide resin composition containing o-hydroxy-trans-cinnamic acid amide as a photobase generator and containing the photobase generator and a base reactive resin. Furthermore, the present inventors also patented a photosensitive polyimide resin composition using an o-hydroxy-trans-cinnamic acid amide derivative as a photocyclization type photobase generator and containing the photobase generator and a polyimide precursor. This is disclosed in Document 5. Patent Documents 6 and 7 disclose a photosensitive polyimide resin composition using a carbamate-type photobase generator. Further, Patent Documents 8 and 9 disclose a photosensitive polyimide resin composition using an oxime type photobase generator.

  A photosensitive polyimide resin composition using a photobase generator is a process for producing a resin composition because a photosensitive polyimide precursor can be obtained simply by mixing a certain amount of a photobase generator with a polyimide precursor. Is simple. Moreover, since it can apply to the polyimide precursor of various structures, there exists an advantage that versatility is high.

JP 52-13315 A JP 54-145794 A JP-A-8-227154 JP 2009-80452 A International Publication No. 2009/123122 Pamphlet JP 2006-189591 A JP 2008-247747 A JP 2007-249013 A JP 2008-003581 A

Chem. Pharm. Bull. 1997, 45 (4) p.715-718

However, the photosensitive polyimide resin composition using the photobase generator as described above develops because imidization of the polyimide precursor proceeds not only in the exposed area but also in the unexposed area in the heating step after exposure. Improvement of sex was an issue. That is, the imidization of the unexposed part also proceeds partially, so that the solubility of the unexposed part in the developer is deteriorated, and there is a problem that the development time must be lengthened. Further, since a basic aqueous solution alone does not sufficiently dissolve as a developing solution, it is necessary to use a basic aqueous solution to which an organic solvent such as alcohol is added. In order to reduce the environmental load, it is required in the market to use a basic aqueous solution without adding an organic solvent such as alcohol as a developer.
Furthermore, when the imidization of the polyimide precursor proceeds excessively in the unexposed area, the dissolution rate contrast between the exposed area and the unexposed area with respect to the developer becomes insufficient, and the relief pattern shape may be deteriorated.

  By relaxing the heating conditions such as lowering the heating temperature during post-exposure baking or shortening the heating time, the progress of imidation of the polyimide precursor in the unexposed area can be suppressed. However, if the heating conditions are relaxed, the progress of imidization is suppressed even in the exposed area, so the solubility contrast between the exposed area and the unexposed area does not improve. Therefore, the present inventors provide a photobase generator that generates a base having a high catalytic ability to sufficiently promote imidation of the polyimide precursor in the exposed portion even if the heating conditions during post-exposure baking are relaxed compared to the conventional one. Focused on getting.

  That is, the present invention has been made in view of the above circumstances, and light that generates a base that sufficiently promotes imidation of a polyimide precursor in an exposed portion even if the heating conditions during post-exposure baking are relaxed as compared with the prior art. An object is to provide a base generator. Further, in the present invention, by using the photobase generator, it is possible to shorten the development time, and it is possible to use a basic aqueous solution to which no alcohol or the like is added as a developer, or to dissolve the exposed and unexposed areas. An object of the present invention is to provide a photosensitive polyimide resin composition having a high optical contrast.

The photo-base generator for a precursor type photosensitive polyimide according to the present invention has the following chemical formula (1-1) or chemical formula (1) in which the generated base is latentized using a covalent bond and generates a base upon irradiation with electromagnetic waves ( It is a base generator represented by 1-2), and the generated base is a secondary amine having a hydroxyl group .

(In formula (1-1), R ¹ And R ² Are each independently an organic group, which may be the same or different. R ¹ And R ² May be bonded to each other to form a cyclic structure, or may contain a heteroatom bond. However, R ¹ And R ² Any of these organic groups has a hydroxyl group. R ³ And R ⁴ Are independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group Group or organic group, which may be the same or different. R ⁵ , R ⁶ , R ⁷ And R ⁸ Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, A phosphonate group, an amino group, an ammonio group, or an organic group, which may be the same or different. R ⁵ , R ⁶ , R ⁷ And R ⁸ In these, two or more of them may be bonded to form a cyclic structure, and may contain a bond of a heteroatom. R ⁹ Is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. )

(In formula (1-2), R ¹ And R ² Are each independently an organic group, which may be the same or different. R ¹ And R ² May be bonded to each other to form a cyclic structure, or may contain a heteroatom bond. However, R ¹ And R ² Any of these organic groups has a hydroxyl group. R ¹⁰ And R ^{10 ’} Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, A phosphonate group, an amino group, an ammonio group, or an organic group, which may be the same or different. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ In these, two or more of them may be bonded to form a cyclic structure, and may contain a bond of a heteroatom. )

  The precursor-type photosensitive polyimide base generator according to the present invention has a high effect of promoting imidization of a polyimide precursor by generating a base having a hydroxyl group by irradiation with electromagnetic waves, and the heating conditions during post-exposure baking are higher than before. Even if relaxed, it is possible to sufficiently promote imidation of the polyimide precursor in the exposed portion.

  In the base generator according to the present invention, it is preferable to generate a base having a hydroxyl group having a boiling point of 150 ° C. or higher and a melting point of 200 ° C. or lower from the viewpoint of increasing the imidization promoting effect of the polyimide precursor.

  In the photobase generator according to the present invention, since the base to be generated is an aliphatic amine, the basicity is strong and the catalytic ability to promote imidization is high. This is preferable because the reaction to the final product is possible.

  In the photobase generator according to the present invention, it is preferable that the generated base does not contain an acidic group from the viewpoint of exhibiting catalytic ability to promote imidization of the generated base.

The negative photosensitive polyimide resin composition according to the present invention comprises a polyimide precursor and the photobase generator according to the present invention.
The negative photosensitive polyimide resin composition according to the present invention uses the photobase generator according to the present invention, so that the exposed area is sufficiently imidized even if the heating conditions during post-exposure baking are more relaxed than before. The unexposed portion can suppress the progress of imidization of the polyimide precursor due to the relaxed heating conditions. Further, dissolution of the unexposed portion in the developer is promoted by the effect of the hydroxyl group introduced into the base. As a result, the solubility of the unexposed area in the developer is improved, so the development time for removing the unexposed area can be shortened, and a basic aqueous solution to which no alcohol or the like is added can be used as the developer. . Furthermore, since the solubility contrast between the exposed portion and the unexposed portion is increased, the shape of the relief pattern is improved.

  In the negative photosensitive polyimide resin composition according to the present invention, the base from which the photobase generator is generated is the polyimide precursor with respect to 100 parts by weight of the base at any temperature of 150 to 200 ° C. It is preferable that it is a base which melt | dissolves 10 weight part or more from the point which improves the catalytic ability of a base.

  The negative photosensitive polyimide resin composition according to the present invention is a paint, a printing ink, a sealant, or an adhesive, or a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped article, an optical member, or an architecture. It is suitably used as a material forming material.

The present invention provides a method for producing a relief pattern using the negative photosensitive polyimide resin composition according to the present invention.
The method for producing a relief pattern according to the present invention comprises forming a coating film or a molded body using the negative photosensitive polyimide resin composition, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, Development is performed after heating or simultaneously with irradiation to change the solubility of the irradiated portion.

  The present invention also provides a printed material, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a micro-electrical device, at least partly formed of the negative photosensitive polyimide resin composition or a cured product thereof. Articles of any of mechanical systems, stereolithography, optical members or building materials are provided.

ADVANTAGE OF THE INVENTION According to this invention, even if the heating conditions at the time of baking after exposure are eased conventionally, the photobase generator which fully accelerates | stimulates the imidation of the polyimide precursor of an exposure part can be provided.
The negative photosensitive polyimide resin composition according to the present invention can shorten the development time, and it is possible to use a basic aqueous solution to which no alcohol or the like is added as a developer, or the solubility contrast between exposed and unexposed areas. Can be high.

It is a graph which shows the relationship between the addition amount of the base with respect to a polyimide precursor, and the imidation ratio in the test example 16, the test example 17, and the comparative test example 11. FIG. It is a sensitivity curve which shows the relationship between the exposure amount of the photosensitive polyimide resin composition of Example 1, Example 2, and the comparative example 1, and a residual film rate. It is a sensitivity curve which shows the relationship between the exposure amount of the photosensitive polyimide resin composition of Example 3 and Comparative Example 2, and a residual film rate.

The present invention will be described in detail below.
In the present invention, (meth) acryloyl means acryloyl and / or methacryloyl, (meth) acryl means acryl and / or methacryl, and (meth) acrylate means acrylate and / or methacrylate. means.
In the present invention, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam, unless the wavelength is specified. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure. Note that electromagnetic waves with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.
In the present invention, the boiling point and melting point refer to the boiling point and melting point under a pressure of 1 atm (101325 Pa).
Moreover, in this invention, an organic group represents the general term of the functional group containing at least 1 carbon atom.

<Photobase generator>
The photo-base generator for a precursor type photosensitive polyimide according to the present invention is a photo-base generator that generates a base by irradiation with electromagnetic waves, wherein the generated base is latentized using a covalent bond, and has a hydroxyl group. It is characterized by generating a base. In addition, a precursor type photosensitive polyimide means here the photosensitive polyimide resin composition containing a polyimide precursor.
The precursor-type photosensitive polyimide base generator according to the present invention generates a base having a hydroxyl group (basic substance) by irradiation with electromagnetic waves, so that even if the heating conditions during post-exposure baking are relaxed compared to conventional exposure, It is possible to sufficiently promote imidation of a part of the polyimide precursor.
Here, the degree of sufficiently promoting imidization of the polyimide precursor in the exposed area is such that the dissolution rate of the polyimide precursor in the exposed area in the developer is sufficiently slow relative to the unexposed area, and is used, for example. It can be taken as a guide that the dissolution rate of the polyimide precursor in the exposed portion with respect to the developing solution is slowed to about 10 nm / s or less at 25 ° C. For example, when a 0.1 to 5.0% by weight tetramethylammonium hydroxide (TMAH) aqueous solution is used as a developer, the imidation ratio of the polyimide precursor in the exposed portion is about 45 to 60%. Is preferred.

  Relaxing the heating conditions during post-exposure bake (PEB) than before, that is, by reducing the heating temperature or shortening the heating time, imidation of the polyimide precursor in the unexposed area is suppressed. Is done. Further, dissolution of the unexposed portion in the developer is promoted by the effect of the hydroxyl group introduced into the base. Due to these synergistic effects, when the photobase generator according to the present invention is used in the precursor type photosensitive polyimide resin composition, the solubility of the unexposed portion in the developer is improved, and the development time for removing the unexposed portion is increased. It can be shortened, and a basic aqueous solution to which no alcohol or the like is added can be used as a developer. Furthermore, while the exposed area is sufficiently imidized, the unexposed area is highly soluble in the developer, so the solubility contrast between the exposed area and the unexposed area is high, and the relief pattern shape is good. become.

  In the photobase generator according to the present invention, the generated base is latentized using a covalent bond. The photobase generator in which the generated base is latentized by using a covalent bond is that the nitrogen atom of the generated base part and the adjacent atom have a covalent bond, and the covalent bond is formed by irradiation with electromagnetic waves. It is a photobase generator that generates bases when cleaved. Since the photobase generator having such a structure can be made neutral, the solvent solubility is good and the pot life is improved. In addition, there is an advantage that the compatibility with the component used in combination with the polyimide precursor is often good.

  Examples of the photobase generator having a structure in which the generated base is latentized using a covalent bond include, for example, a base generator having a cinnamic acid amide structure as disclosed in Patent Documents 5 and 6, and the above patent. Examples include base generators having a carbamate structure as disclosed in Documents 7 and 8, oxime structures as disclosed in Patent Documents 9 and 10 above, base generators having a carbamoyloxime structure, and the like. In addition, other known photobase generator structures can be used.

  The photobase generator according to the present invention generates a base having a hydroxyl group. When the generated base has a hydroxyl group, the polyimide precursor described later can be efficiently imidized even when the post-exposure baking temperature is set lower than before or the heating time is shortened. A compound having an amino group and a hydroxyl group in one molecule has a high affinity with polyimide and a polyimide precursor, and in the process of imidization of the polyimide precursor in the coating film, the state of imidization has progressed to a pseudo state. It is presumed that it functions as a solvent and a catalyst that promotes imidization. Furthermore, when the generated base has a hydroxyl group, the solubility of the unexposed portion in the basic aqueous solution tends to be improved. This is presumably because the hydroxyl group bonded to the base latent in the photobase generator improves the solubility in a basic aqueous solution by interacting with the polyimide precursor. In addition, what is necessary is just to have one or more hydroxyl groups, and the structure of the base to generate | occur | produce is not specifically limited. The phenolic hydroxyl group is preferably an alcoholic hydroxyl group from the viewpoint that it becomes a weak acidic group. The alcoholic hydroxyl group means a hydroxyl group directly bonded to the aliphatic hydrocarbon skeleton, and the phenolic hydroxyl group means a hydroxyl group directly bonded to the aromatic hydrocarbon skeleton.

Moreover, it is preferable that the base to generate | occur | produce is a base which has a hydroxyl group whose boiling point is 150 degreeC or more and melting | fusing point is 200 degrees C or less from the point that the imidation promotion effect of a polyimide precursor becomes high.
The heating temperature required for imidization of a polyimide precursor having a general structure is 140 ° C. or higher, and the post-exposure heating temperature is usually selected within the range of 140 ° C. to 210 ° C. in many cases.
When the boiling point of the generated base is 150 ° C. or higher, volatilization of the base in the post-exposure heating step is suppressed, and the generated base can be efficiently used as an imidization promoting catalyst. Among them, the boiling point is preferably 160 ° C. or higher. Further, if the melting point is 200 ° C. or less, the base is liquid in the post-exposure heating step, and it is easier to diffuse in the resin composition than in the case of a solid, or it functions as a pseudo solvent, and polyimide The degree of freedom of the molecular chain of the precursor can be improved. Therefore, it is presumed that imidation of the polyimide precursor can be efficiently promoted even with a small amount of base. Among these, the melting point is preferably 190 ° C. or lower.

  In the photobase generator according to the present invention, the generated base is latentized using a covalent bond, and thus the generated base includes a primary amine, a secondary amine, or a heterocyclic compound. The amine includes an aliphatic amine and an aromatic amine, respectively. In addition, among amines, the case where at least one aromatic group is directly bonded to the nitrogen atom of the amine is referred to as an aromatic amine, and the other case is included in the aliphatic amine. Moreover, the heterocyclic compound here means that the base has a cyclic structure and has aromaticity. Non-aromatic heterocyclic compounds that are not aromatic heterocyclic compounds are included here in aliphatic amines as alicyclic amines.

Furthermore, the generated base is not only a base such as a monoamine having only one NH group capable of forming an amide bond but also a base having two or more NH groups capable of forming an amide bond such as diamine, triamine and tetraamine. There may be. Among these, those having one NH group capable of forming an amide bond are preferable from the viewpoints of base generation efficiency, solvent solubility, and purification in synthesis.
An example of the generated base is shown below, but is not limited thereto.

  Examples of aliphatic primary amines include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, and 2-amino-1-butanol. 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2- Amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4- ( 2-aminoethyl) cyclohexanol and the like.

  As the aliphatic secondary amine, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, α- [2- (methylamino) ethyl] Benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4- (3-hydroxyphenyl) piperidine, 4-piperidine Examples include methanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2- (4-piperidyl) -2-propanol, and alicyclic amine is particularly preferable.

  As aromatic primary amines, 4-aminophenol, 3-aminophenol, 2-aminophenol, 4-aminobenzyl alcohol, 3-aminobenzyl alcohol, 2-aminobenzyl alcohol, 2- (4-aminophenyl) ethanol Etc.

  Examples of aromatic secondary amines include 2-anilinoethanol, 3-anilino-1-propanol, 4-hydroxydiphenylamine, 3-hydroxydiphenylamine, 3,3'-dihydroxydiphenylamine, 4-benzylaminophenol, and the like. In addition, as an aromatic heterocyclic compound having an NH group capable of forming an amide bond, an imino bond (—N═C (—R) —, —C (═NR) —, Here, R preferably has a hydrogen atom or an organic group, and examples thereof include derivatives in which a hydroxyl group is substituted with imidazole, purine, or triazole. Among these, a photobase generator in which all basic sites in the base are latently neutral is preferable.

  Catalysis that lowers the reaction start temperature for the reaction from the polyimide precursor to the final product is that the base having a higher basicity is more effective as a catalyst, and the final product at a lower temperature with a smaller amount added It becomes possible to react to In general, aliphatic amines are more basic than aromatic amines, and thus have higher catalytic ability. Therefore, in the photobase generator according to the present invention, the generated base is preferably an aliphatic amine. In addition, when the generated base is an aliphatic amine, it is easy to volatilize quickly after completion of imidation, and when imidized under the same heating conditions, compared to basic aromatic heterocyclic compounds and amidines, It is also preferable from the point of little remaining in the coating film.

  In addition, when the base generated in the present invention is a secondary amine and / or a heterocyclic compound, it is preferable from the viewpoint of increasing the sensitivity as a photobase generator. It is presumed that this is because the use of a secondary amine or a heterocyclic compound eliminates active hydrogen at the amide bond site, thereby changing the electron density and improving the sensitivity of isomerization.

  Furthermore, it is preferable that the base generated from the photobase generator according to the present invention does not contain an acidic group from the viewpoint of not reducing the catalytic ability of the generated base. However, a photobase generator that generates a base containing a weak acidic group such as a phenolic hydroxyl group may be used in the photobase generator of the present invention because it does not reduce the catalytic ability of the base. The acidic group preferably does not contain a strong acidic group such as a carboxyl group, a sulfo group, and a phosphoric acid group.

  In the photobase generator according to the present invention, the presence of a base is a photobase generator represented by the following chemical formula (1-1), the following chemical formula (1-2), or the following chemical formula (1-3). It is preferable because it can be used for various polyimide precursors whose reaction to the final product is accelerated by heating under. Among these, it is a photobase generator represented by the following chemical formula (1-1) because it has excellent sensitivity and can obtain a pattern having a good shape regardless of the type of polyimide precursor. preferable.

(In Formula (1-1), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. At least one of R ¹ and R ² is organic. R ¹ and R ² may be bonded to each other to form a cyclic structure, and may contain a heteroatom bond, provided that any one of R ¹ and R ² is an organic group Each of R ³ and R ⁴ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, A phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group, which may be the same or different, and each of R ⁵ , R ⁶ , R ^7, and R ⁸ independently represents a hydrogen atom, a halogen atom, atom, Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to form a cyclic structure by combining two or more of R ⁵ , R ⁶ , R ⁷ and R ^8. R ⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

(In Formula (1-2), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. At least one of R ¹ and R ² is organic. R ¹ and R ² may be bonded to each other to form a cyclic structure, and may contain a heteroatom bond, provided that any one of R ¹ and R ² is an organic group Each of R ¹⁰ and R ^{10 ′} independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group or an organic group, which may be the same or different, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are those 2 Two or more may be bonded to form a cyclic structure, and may include a heteroatom bond.)

(In formula (1-3), R ¹⁷ is an amino group substituted with an organic group having a hydroxyl group or an organic group having a hydroxyl group, and R ¹⁸ and R ¹⁹ are independently a hydrogen atom, a halogen atom, or a sulfide group. , Silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group or organic group, may be different ^{but, .R 17, R 18} and ^{R 19} at least one is aromatic compound which may have a hetero atom of ^{R 18} and ^{R 19} are, those two or more bonded May form a cyclic structure and may include a bond of a hetero atom.)

When the photobase generator represented by the chemical formula (1-1) is irradiated with electromagnetic waves, the formula (1-1) in the formula (-CR ⁴ = CR ^3- The C (= O)-) moiety isomerizes from the trans form to the cis form. Further, when R ⁹ is a protecting group by heating and / or irradiation with electromagnetic waves, the protecting group R ⁹ is deprotected and cyclized to produce a base (NHR ¹ R ² ). The photobase generator represented by the formula (1-1) generates a base only by irradiation with electromagnetic waves, but generation of the base is promoted by heating appropriately.

In addition, when the photobase generator represented by the chemical formula (1-2) is irradiated with electromagnetic waves, the bond is cleaved by a photodecarboxylation reaction of a carbamate bond to generate a base (NHR ¹ R ² ).
Furthermore, the photobase generator represented by the above chemical formula (1-3) is an oxime ester derivative, and causes an intramolecular cleavage reaction by absorption of electromagnetic waves according to the following reaction formula to generate amine or hydrazine.

In the above chemical formula (1-1) and chemical formula (1-2), R ¹ and R ² are each independently a hydrogen atom or an organic group, but at least one of R ¹ and R ² is an organic group. is there. Further, NHR ¹ R ² is a base, but R ¹ and R ² are each preferably an organic group not containing an amino group. If an amino group is contained in R ¹ and R ² , the photobase generator itself becomes a base, which accelerates the reaction of the polyimide precursor, resulting in a difference in solubility contrast between the exposed and unexposed areas. There is a risk of becoming smaller. However, when there is a difference in basicity between the electromagnetic wave irradiation and the base generated after heating, such as when an amino group is bonded to the aromatic ring present in the organic group of R ¹ and R ^2. May be used even if the organic group of R ¹ and R ² contains an amino group.
Examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic.
The organic group is preferably a linear, branched or cyclic hydrocarbon group which may contain a substituent, may contain an unsaturated bond, and may contain a heteroatom bond.
The organic group in R ¹ and R ² is usually a monovalent organic group, but in the case of forming a cyclic structure described later, the generated NHR ¹ R ² is an NH group capable of forming an amide bond such as diamine. In the case of a base having two or more, it can be a divalent or higher valent organic group.
Any one of R ¹ and R ² has a hydroxyl group. If the organic group has one or more hydroxyl groups, they may be present anywhere in the organic group. When R ¹ and R ² form a cyclic structure, the cyclic structure may have one or more hydroxyl groups. When either organic group of R ¹ and R ² has a hydroxyl group, the photobase generator generates a base having a hydroxyl group. When the base has a hydroxyl group, the catalytic ability is improved and the heating conditions during post-exposure baking can be relaxed. For example, the polyimide precursor described later can be efficiently imidized even at a lower temperature.

R ¹ and R ² may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond. Amide bond, urethane bond, imino bond (-N = C (-R)-, -C (= NR)-, where R is a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond Etc. From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (— R)-, -C (= NR)-: where R is a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond.

Substituents other than the hydrocarbon group in the organic group of R ¹ and R ² , that is, substituents included in the organic group, which are different from the hydrocarbon group, and may be substituted with a hydrocarbon group. The substituent is not particularly limited as long as the effects of the present invention are not impaired. The substituent is a halogen atom, a mercapto group (—SH), a sulfide group (—SR, where R is an organic group), a cyano group (—CN). , Isocyanato group (-NCN), isocyanato group (-OCN), isocyanato group (-NCO), thiocyanato group (-SCN), isothiocyanato group (-NCS), alkyl ether group and aryl ether group (-OR, where R Is an organic group), an alkoxycarbonyl group and an aryloxycarbonyl group (—COOR, where R is an organic group), an alkylsulfinyl group and an arylsulfinyl group ( SOR, where R is an organic group), an alkylsulfonyl group and an arylsulfonyl group _(-SO 2 R, where R is an organic group), alkoxy sulfonyl group, and an aryloxy sulfonyl group _(-SO 3 R, where R is an organic Group), carbamoyl group (—CONRR ′, where R and R ′ are organic groups), thiocarbamoyl group (—CSNRR ′, where R and R ′ are organic groups), sulfamoyl group (—SO ₃ NRR ′, where R, R ′ are organic groups), nitro group (—NO ₂ ), nitroso group (—NO), acyl group (—COR, where R is an organic group), acyloxy group (—OCOR, where R is an organic group) Group), acylamino group (—NHCOR, where R is an organic group), carbamate group (—NHCOOR, where R is an organic group), phosphino group (—PR ₂ ), silyl group (—SiR ₃ , where R is Organic group), alkoxysilyl group and aryloxysilyl group (—Si (OR) _X R ′ _Y , where R and R ′ are organic groups, X is an integer of 1 to 3, Y is an integer of 0 to 2, X + Y = 3), amino groups (-NH2, -NHR, -NRR ': where R and R' are each independently a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
Substituents different from the hydrocarbon group and hydroxyl group in the organic group of R ¹ and R ² include a halogen atom, a mercapto group (—SH), a sulfide group (—SR, where R is an organic group), a cyano group. (-CN), isocyano group (-NC), cyanato group (-OCN), isocyanato group (-NCO), thiocyanate group (-SCN), isothiocyanato group (-NCS), alkyl ether group and aryl ether group (-OR) Where R is an organic group), an alkoxycarbonyl group and an aryloxycarbonyl group (—COOR, where R is an organic group), a sulfinyl group (—SOR, where R is an organic group), an alkylsulfonyl group, and an arylsulfonyl group _(-SO 2 R, where R is an organic group), alkoxy sulfonyl group, and an aryloxy sulfonyl group _(-SO 3 R, where Organic groups), a carbamoyl group (-CONRR ', wherein R, R' is an organic group), a thiocarbamoyl group (-CSNRR ', wherein R, R' is an organic group), a sulfamoyl group _(-SO 3 NRR ' Where R and R ′ are organic groups), nitro groups (—NO ₂ ), nitroso groups (—NO), acyl groups (—COR, where R is an organic group), acyloxy groups (—OCOR, where R Is an organic group), acylamino group (—NHCOR, where R is an organic group), carbamate group (—NHCOOR, where R is an organic group) silyl group (—SiR ₃ , where R is an organic group), alkoxysilyl group And an aryloxysilyl group (—Si (OR) _X R ′ _Y , wherein R and R ′ are organic groups, X is an integer of 1 to 3, Y is an integer of 0 to 2, and X + Y = 3). .
A structure in which a bond other than the hydrocarbon group or a hydrogen atom or an organic group in a substituent other than the hydrocarbon group is substituted with a hydroxyl group may be used.

The thermal properties of the base generated, and from the viewpoint of basicity, organic groups R ¹ and R ² is preferably 1 to 20 carbon atoms each independently, more preferably 1 to 12 carbon atoms, particularly carbon atoms It is preferable that it is 1-8.
Since the generated base is NHR ¹ R ² , primary amines, secondary amines, or heterocyclic compounds can be mentioned. As a suitable example of the generated base, it has been described above, and the description thereof is omitted here.

In the chemical formula (1-1), R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, A sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group, which may be the same or different.
R ³ and R ⁴ are each preferably a hydrogen atom from the viewpoint of easily achieving high sensitivity.

In the present invention, in particular, when at least one of R ³ and R ^{4 in} the chemical formula (1-1) is not a hydrogen atom but the specific functional group, both R ³ and R ⁴ are hydrogen. Compared to the case of atoms, the photobase generator of the present invention can further improve the solubility in an organic solvent or improve the affinity with a polyimide precursor. For example, when at least one of R ³ and R ⁴ is an organic group such as an alkyl group or an aryl group, the solubility in an organic solvent is improved. For example, when at least one of R ³ and R ⁴ is a halogen atom such as fluorine, the affinity with a polyimide precursor containing a halogen atom such as fluorine is improved. As described above, R ³ and / or R ⁴ are combined with a desired organic solvent or polyimide precursor, and a substituent is appropriately introduced to thereby dissolve in a desired organic solvent and have an affinity with a desired polyimide precursor. It is possible to improve.

The halogen atom, organic group, as long as the effects of the present invention are not impaired, it is not particularly limited, and may be the same as those listed ^{R 5 ~R 8, R 11 ~R} 15 to be described later.
The organic group in R ³ and R ⁴ is usually a monovalent organic group.

When R ³ and R ⁴ have a substituent, at least one of them is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; a C 4 to 23 carbon atom such as a cyclopentyl group or a cyclohexyl group. A cycloalkyl group; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group (-ROAr group); Aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; Alkyl group having 2 to 21 carbon atoms having cyano group such as cyanomethyl group and β-cyanoethyl group; Hydroxymethyl group C1-C20 alkyl groups having a hydroxyl group such as, methoxy groups, ethoxy groups, etc., C1-C20 alkyl ether groups , Acetamido group, benzenesulfonyl cyanamide group - sulfide such as an amide group having a carbon number of 2 to 21, such as a methylthio group, an alkylthio group having 1 to 20 carbon atoms such as an ethylthio group _{(C 6 H 5 SO 2 NH} 2) Group (-SR group), acyl group having 1 to 20 carbon atoms such as acetyl group and benzoyl group, ester group having 2 to 21 carbon atoms such as methoxycarbonyl group and acetoxy group (-COOR group and -OCOR group), phenyl Group, naphthyl group, biphenyl group, tolyl group and the like, an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or Or it is preferable that they are the benzyl group and cyano group which the electron withdrawing group substituted. The alkyl moiety may be linear, branched or cyclic.

In the chemical formula (1-2), R ¹⁰ and R ^{10 ′} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group. For example, the same as those mentioned in R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described later can be used.

R ^{5 to} R ⁸ in the chemical formula (1-1) and R ^{11 to} R ¹⁵ in the chemical formula (1-2) are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, or a sulfide group. Silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group, It may be different. Two or more of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a cyclic structure, or may include a hetero atom bond.

It is preferable to introduce one or more substituents into R ^{5 to} R ⁸ in the chemical formula (1-1) and R ^{11 to} R ¹⁵ in the chemical formula (1-2). In particular, in the case of the base generator represented by the above chemical formula (1-1), the double bond between the α carbon and β carbon located at the α-position and β-position of the carbonyl bond is an isomerization reaction from a trans isomer to a cis isomer. There are several factors that promote the efficiency of the reaction, for example, the size of the steric hindrance around the carbon-carbon double bond, the electronic state of the conjugated chain extending around the carbon-carbon double bond, and the like. By introducing at least one substituent as described above into R ^{5 to} R ⁸ , the conjugated chain around the carbon-carbon double bond is expanded, and the base generation sensitivity can be improved. In R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , the wavelength of light to be absorbed can be adjusted by introducing at least one substituent as described above, and the substituent is introduced. It is also possible to absorb the desired wavelength. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. Moreover, solubility and compatibility with the polyimide precursor to be combined can be improved. Thereby, it is possible to improve the sensitivity of the photosensitive polyimide resin composition in consideration of the absorption wavelength of the polyimide precursor to be combined.

  As a guideline of what substituents should be introduced to shift the absorption wavelength with respect to a desired wavelength, the Interspection of the Ultraviolet Products (AI Scott 1964) and the spectrum of organic compounds The table described in the identification method 5th edition (RM Silverstein 1993) can be referred to. By referring to these, it is possible to know a measure of how long the maximum absorption wavelength of the compound is increased.

R ^{11 in the} chemical formula (1-2) is preferably a nitro group from the viewpoint of improving the sensitivity of the photobase generator represented by the chemical formula (1-2).

In R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , examples of the halogen atom include fluorine, chlorine, bromine and the like.
In R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. Etc. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic. As the bond other than the hydrocarbon group in the organic groups of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , the same bond as the bond other than the hydrocarbon group of R ¹ and R ² can be used. ^The organic group of R 5 to R ⁸ and ^R 11 ^{to R 15} may be bonded to the benzene ring via a bond other than a hydrocarbon group. Further, in the organic groups of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , substituents other than hydrocarbon groups (substituents included in the organic groups are substituted with substituents different from hydrocarbon groups, and hydrocarbon groups). As the substituent which may be present, the same substituents as those other than the hydrocarbon groups of R ¹ and R ² can be used.
The organic group is not particularly limited as long as the effect of the present invention is not impaired, and is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. , Cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, saturated or unsaturated Examples thereof include a saturated alkyl ether group, a saturated or unsaturated alkylthio group, an aryl ether group, and an arylthio group.
The organic group in R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ is usually a monovalent organic group, but may form a divalent or higher organic group when forming a cyclic structure to be described later.

Two or more of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient. For example, each of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ is bonded to two or more of them, and an atom of a benzene ring to which each of R ^{5 to} R ⁸ and each of R ^{11 to} R ¹⁵ is bonded. It may be shared to form a condensed ring such as naphthalene, anthracene, phenanthrene or indene.

R ^{5 to} R ⁸ or R ^{11 to} R ¹⁵ are hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino Group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, methyl group, ethyl group, propyl group and other alkyl groups having 1 to 20 carbon atoms; cyclopentyl group, cyclohexyl group and the like having 4 to 23 carbon atoms An alkyl group; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group ( -ROAr group); aralkyl having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group An alkyl group having 2 to 21 carbon atoms having a cyano group such as a cyanomethyl group or a β-cyanoethyl group; an alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group, a methoxy group, an ethoxy group, or benzyloxy An alkyl ether group which may be substituted with an aryl group having 1 to 20 carbon atoms such as a group; an aryl ether group such as a phenoxy group or a naphthyloxy group; an acetamide group or a benzenesulfonamide group (C ₆ H ₅ SO ₂ NH _2- ) an amide group having 2 to 21 carbon atoms, such as an alkylthio group having 1 to 20 carbon atoms (-SR group) such as a methylthio group or an ethylthio group, an arylthio group such as a benzylthio group or a naphthylthio group; an acetyl group or a benzoyl group An acyl group having 1 to 20 carbon atoms such as thioacyl group; an acylthio group such as acetylthio group or benzoylthio group; C2-20 aryl such as bonyl group, acetoxy group, benzyloxycarbonyl group, etc., C2-C21 ester group (—COOR group and —OCOR group), phenyl group, naphthyl group, biphenyl group, tolyl group, etc. Group, an aryl group having 6 to 20 carbon atoms substituted with an electron donating group and / or an electron withdrawing group, a benzyl group substituted with an electron donating group and / or an electron withdrawing group, a cyano group, a carbamoyl group, It is preferably a carbamoyloxy group, a cyanooxy group (cyanato group), a cyanothio group (thiocyanato group), or a formyl group. The alkyl moiety may be linear, branched or cyclic.
^As the R 5 to R ⁸ or ^R 11 ^{to R 15,} and two or more of them are ^combined, share the atoms of the benzene ring of R 5 to R ⁸ or ^R 11 ^{to R 15} are bonded A condensed ring such as naphthalene, anthracene, phenanthrene, and indene is also preferable from the viewpoint of increasing the absorption wavelength.

In Formula (1-1), R ⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. Here, “deprotectable” means that there is a possibility of changing from —OR ⁹ to —OH. When R ⁹ is a hydrogen atom, the photobase generator according to the present invention is cyclized so that the phenolic hydroxyl group disappears and the solubility is changed. descend. Thereby, it has the function of further assisting the decrease in solubility due to the reaction of the polyimide precursor to the final product, and the solubility contrast between the exposed portion and the unexposed portion can be further increased.

In addition, when R ⁹ is a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves, it is deprotected by heating and / or irradiation with electromagnetic waves to generate a hydroxyl group. By protecting the phenolic hydroxyl group with a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves, the compatibility with the polyimide precursor is improved by selecting the protecting group as appropriate. The range increases. For example, it is possible to use a polyimide precursor that is not preferable to coexist with a phenolic hydroxyl group in the photosensitive polyimide resin composition. R ⁹ is a phenolic hydroxyl group that can be deprotected by heating and / or irradiation with electromagnetic waves under the condition that the amide group present in Formula (1-1) does not decompose in the photobase generator used in the present invention. Any group can be used without particular limitation. For example, an amide bond is a strong acid such as boron tribromide or aluminum trichloride, a strong Lewis acid such as sulfuric acid, hydrochloric acid or nitric acid, or a strong base such as sodium hydroxide. Decomposes on heating under basic conditions. Therefore, such a protecting group that can be deprotected only by heating under strongly acidic or strongly basic conditions is inappropriate as a protecting group for use in the photobase generator of the present invention. R ⁹ depends on the type of compound used in combination with the photobase generator, the application method of the photobase generator, and the synthesis method for the purpose of improving solubility and compatibility or changing the reactivity during synthesis. It is appropriately selected.

R ⁹ can be selected from silyl groups, silanol groups, phosphino groups, phosphinyl groups, phosphono groups, or organic groups. The organic group in R ⁹ is usually a monovalent organic group.

R ⁹ is present in the formula (1-1) to be at least one selected from the group consisting of organic groups represented by the following formulas (2-1) to (2-6). It is preferable from the viewpoint that it can be deprotected by heating and / or irradiation with electromagnetic waves under conditions where the amide group does not decompose.

(In the formula (2-1), R ³⁰ , R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom or an organic group, R ³³ is an organic group, and R ³⁰ , R ³¹ , R ³² , R ³³ may be bonded to each other to represent a cyclic structure, and in formula (2-2), R ³⁴ is an organic group, and in formula (2-3), R ³⁵ , R ³⁶ , R ³⁷ Each independently represents a hydrogen atom, a halogen atom, or an organic group, wherein R ³⁸ is an organic group, and R ³⁹ has a substituent in formula (2-5). (In formula (2-6), R ⁴⁰ is an organic group.)

The organic group represented by the above formula (2-1) can be obtained by a reaction between a hydroxyl group and various vinyl ether compounds. The organic group represented by the formula (2-1) is, for example, a residue of various vinyl ether compounds.
The organic group represented by the above formula (2-2) includes, for example, a hydroxyl group and a reagent for introducing a carbonate-based protecting group (for example, di-t-butyl dicarbonate, benzyloxycarbonyl chloride, N- (9-flurane). Olenylmethoxycarbonyloxy) succinimide and the like). The organic group represented by Formula (2-2) is, for example, a residue of various carbonate-based protecting groups.
The organic group represented by the above formula (2-3) is, for example, a reaction between a hydroxyl group and a reagent for introducing a silyl ether protecting group (for example, chlorotrimethylsilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, etc.) Can be obtained. The organic group represented by the formula (2-3) is, for example, a residue of a silyl ether protecting group.

The organic group represented by the above formula (2-4) can be obtained, for example, by a reaction between a hydroxyl group and an acid chloride or acid anhydride. The organic group represented by the formula (2-4) is: Residue of acid chloride or acid anhydride.
The organic group represented by the above formula (2-5) can be obtained from a hydroxyl group and a halide (for example, benzyl chloride) using, for example, the Williamson reaction, and represented by the formula (2-5). An organic group is a residue of a halide.
The organic group represented by the above formula (2-6) can be obtained, for example, by a reaction between a hydroxyl group and an isocyanate compound (for example, benzyl isocyanate). The organic group represented by the formula (2-6) is , A residue of an isocyanate compound.

  The structure represented by the chemical formula (1-1) has a geometric isomer, but it is preferable to use only the trans isomer. However, cis isomers that are geometric isomers may be mixed during synthesis and purification steps and storage, and in this case, a mixture of trans isomer and cis isomer may be used. It is preferable that the ratio of cis-isomer is less than 10%.

In the chemical formula (1-3), R ¹⁷ is an amino group substituted with an organic group having a hydroxyl group or an organic group having a hydroxyl group. When R ¹⁷ is an organic group having a hydroxyl group, a structure in which a hydroxyl group is appropriately substituted with an organic group similar to the organic groups listed in R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ can be used.
When R ^{17 in the} chemical formula (1-3) is an amino group substituted with an organic group having a hydroxyl group, it has a carbamoyloxime structure represented by the following formula (1-3 ′), as described above. Can generate amines and hydrazines.

(In the formula (1-3 ′), R ¹⁸ and R ¹⁹ are the same as those in the chemical formula (1-3), and R ²⁰ and R ²¹ are the same as R ¹ and R ^{2 in} the chemical formula (1-1). R ¹⁸ , R ¹⁹ , R ^20, and R ²¹ may be bonded to each other to form a cyclic structure, and may include a hetero atom bond, provided that R ²⁰ And any organic group of R ²¹ has a hydroxyl group.)

In the above chemical formulas (1-3) and (1-3 ′), at least one of R ¹⁸ and R ^{19 is} an aromatic compound which may have a hetero atom. The state in which at least one of R ¹⁸ and R ¹⁹ is substituted with an aromatic compound refers to a state in which the aromatic compound is directly covalently bonded to the carbon to which R ¹⁸ and R ¹⁹ are bonded. Say. Here, the aromatic compound refers to a cyclic unsaturated organic compound, and includes aromatic hydrocarbons and aromatic heterocyclic compounds. Examples of the aromatic compound include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorene group, an anthranyl group, a phenanthrenyl group, and a pyrenyl group, as well as a furanyl group, a thiophenyl group, and a pyrrolyl group. And heteroaromatic compounds such as (thio) xanthenyl group, (thio) xanthonyl group, coumaryl group, anthraquinolyl group, and the like. The substituent which these may have may be the same as R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described above. When one of R ¹⁸ and R ¹⁹ is an organic group other than an aromatic compound, it may be the same as R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described above.

In the above chemical formulas (1-3) and (1-3 ′), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ may be bonded to each other to form a cyclic structure. It may also contain a heteroatom bond. Examples of the case where R ¹⁸ and R ¹⁹ are bonded to form a cyclic structure include an embodiment in which a fluorene ring is formed together with the carbon to which R ¹⁸ and R ¹⁹ are bonded. Further, when R ¹⁸ and R ¹⁷ or R ¹⁸ and R ²⁰ are bonded to form a cyclic structure, for example, R ¹⁸ and R ¹⁷ , R ¹⁸ and R ²⁰ are an aliphatic hydrocarbon group and / or The aspect connected with the aromatic hydrocarbon group is mentioned.
Since the base to be generated has a hydroxyl group, any organic group of R ²⁰ and R ²¹ has a hydroxyl group. Since R ²⁰ and R ²¹ are the same as R ¹ and R ^{2 in} the chemical formula (1-1), description thereof is omitted here.
Although an example of the photobase generator of this invention is shown below, it is not limited to these.

The photobase generator according to the present invention preferably has a temperature (5% weight reduction temperature) of 5% by weight or less when heated to 5% by weight or less, more preferably 100 ° C or more. It is preferable. In the case of a polyimide precursor, it is necessary to use a high boiling point solvent such as N-methyl-2-pyrrolidone when forming a coating film. The coating film can be formed under such a drying condition as to decrease. Thereby, the reduction | decrease of the solubility contrast by the influence of a residual solvent in an exposed part and an unexposed part can be suppressed.
In the present invention, the x% weight reduction temperature is the time when the weight of the sample is reduced by x% from the initial weight when the weight loss is measured using a thermogravimetric analyzer (ie, the sample weight is the initial (100−x )%)).

The photobase generator of the present invention can be synthesized by a plurality of conventionally known synthesis routes. The photobase generator represented by the chemical formula (1-1) can be synthesized with reference to, for example, Patent Document 5 and Japanese Patent Application No. 2010-176384 by the present inventors. In the photobase generator represented by the chemical formula (1-1), the protecting group (R ⁹ ) in the phenolic hydroxyl group may be introduced during the synthesis or even at the end of the synthesis. good. Moreover, the photobase generator represented by the chemical formula (1-2) can be synthesized with reference to, for example, Patent Documents 6 and 7. Moreover, the photobase generator represented by the chemical formula (1-3) can be synthesized with reference to, for example, the above-mentioned Patent Documents 8 and 9.

  The photobase generator of the present invention needs to have an absorption for at least a part of the exposure wavelength in order to fully exhibit the function of base generation for the polyimide precursor to be the final product. The wavelength of a high-pressure mercury lamp that is a general exposure light source includes 365 nm, 405 nm, and 436 nm. For this reason, it is preferable that the photobase generator used in the present invention absorbs electromagnetic waves having at least one wavelength among electromagnetic waves having wavelengths of at least 365 nm, 405 nm, and 436 nm. In such a case, it is preferable because the number of applicable polyimide precursors is further increased.

  The photobase generator of the present invention preferably has a molar extinction coefficient of 100 or more at an electromagnetic wave wavelength of 365 nm or 1 or more at 405 nm from the viewpoint of further increasing the types of applicable polyimide precursors.

The fact that the photobase generator of the present invention has absorption in the wavelength region means that the photobase generator of the present invention is 1 × 10 ^{−4 in a} solvent that does not absorb in the wavelength region (for example, acetonitrile). It is dissolved at a concentration of mol / L or less (usually about 1 × 10 ⁻⁴ mol / L to 1 × 10 ⁻⁵ mol / L. It may be appropriately adjusted so as to obtain an appropriate absorption intensity). It can be clarified by measuring the absorbance with an ultraviolet-visible spectrophotometer (for example, UV-2550 (manufactured by Shimadzu Corporation)).

  The photobase generator of this invention is used suitably as a photobase generator for precursor type photosensitive polyimides for preparing a photosensitive polyimide resin composition in combination with a polyimide precursor described later. However, the photobase generator of the present invention can be used to prepare a photosensitive resin composition in combination with other polymer precursors whose reaction to the final product is accelerated by a base or by heating in the presence of a base. You can also.

<Photosensitive polyimide resin composition>
The negative photosensitive polyimide resin composition according to the present invention comprises a polyimide precursor and the photobase generator according to the present invention.
When the negative photosensitive polyimide resin composition according to the present invention is exposed, a base is generated from the photobase generator, and the exposed portion is imidated at the time of post-exposure baking by the catalytic action of the base. Is promoted compared to the unexposed area, and imidization can proceed at a lower temperature. In order to obtain a pattern using the negative photosensitive polyimide resin composition of the present invention, imidation proceeds in a place where a base exists after exposure to a place where the pattern is to be left, and in a place where no base exists. Heating is performed at a temperature at which imidization hardly proceeds. Thereby, the solubility with respect to the developing solution of an exposed part falls, and an exposed part remains after image development.

  The negative photosensitive polyimide resin composition according to the present invention uses the photobase generator according to the present invention, so that the exposed area is sufficiently imidized even if the heating conditions during post-exposure baking are relaxed compared to the conventional one. The unexposed portion can suppress the progress of imidization of the polyimide precursor due to the relaxed heating conditions. Further, dissolution of the unexposed portion in the developer is promoted by the effect of the hydroxyl group introduced into the base. Due to the synergistic effect of relaxed heating conditions and hydroxyl group dissolution, the solubility of the unexposed area in the developer is improved, so the development time for removing the unexposed area can be shortened, and no base is added to the alcohol. Aqueous solution can be used as a developer. Furthermore, while the exposed area is sufficiently cured, the solubility of the unexposed area in the developer is high, so the solubility contrast between the exposed area and the unexposed area is increased, so that the relief pattern has a good shape. Become.

Hereinafter, the components of the photosensitive polyimide resin composition according to the present invention will be described in order of a polyimide precursor, a photobase generator, and other components that can be appropriately included as necessary.
As a photobase generator and a polyimide precursor, you may use individually by 1 type, and may mix and use 2 or more types.

(Polyimide precursor)
The polyimide precursor used in the photosensitive polyimide resin composition of the present invention means a substance that finally becomes a polyimide that exhibits the desired physical properties by reaction.
As the polyimide precursor used in the present invention, one that is soluble in any solvent (organic solvent or aqueous solution) is preferably used. If it is soluble in a solvent (an organic solvent or an aqueous solution), the solubility of the polyimide precursor in the solvent is changed, and the soluble solvent is used as a developer. It is possible to perform development with a neutral aqueous solution, an acidic aqueous solution, or a neutral aqueous solution.
Here, “soluble in a certain solvent” specifically means that the dissolution rate of the coating film formed on the substrate at 25 ° C. in the solvent is 10 nm / sec or more. The dissolution rate is more preferably 30 nm / sec or more from the viewpoint of process suitability.

  For example, what is soluble in a basic aqueous solution specifically has a dissolution rate of a coating film formed on a substrate in a 0.1 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. of 10 nm / sec or more. It is. The dissolution rate is further preferably 30 nm / sec or more. Furthermore, the dissolution rate in a 2.38% by weight tetramethylammonium hydroxide aqueous solution, which is a more commonly used developer, is preferably 10 nm / sec or more, and more preferably 30 nm / sec or more. . When the dissolution rate according to the above definition is less than 10 nm / sec, the development time is delayed, workability and productivity are deteriorated, and it is difficult to obtain a solubility contrast between the exposed and unexposed areas.

  As a specific procedure for measuring the dissolution rate, a polyimide precursor coating film formed on a substrate such as an alkali-free glass was adjusted to 25 ° C. and stirred with a developer (0.1 wt% TMAH). Difference between the initial film thickness and the film thickness measured after being immersed in an aqueous solution or a basic aqueous solution such as a 2.38 wt% TMAH aqueous solution, an organic solvent, etc., rinsed with distilled water and dried. Is the amount of film reduction, and the amount of film reduction divided by the time immersed in the developer is the dissolution rate per unit time at 25 ° C.

Further, in order to obtain a sufficient solubility contrast between the exposed portion and the unexposed portion, when the photosensitive polyimide resin composition is actually used in a predetermined photosensitive pattern forming process, pattern exposure and heating steps are performed. The ratio of the solubility of the unexposed part and the exposed part in the developer before the development step (dissolution rate per unit time in the developer at the unexposed part / dissolution rate per unit time in the developer at the exposed part) ) Is preferably 5 or more, more preferably 10 or more.
The dissolution rate per unit time is determined in the same manner as in the above method. After the pattern exposure is performed on the coating film of the photosensitive polyimide resin composition and the heating after the exposure is performed, the exposed portion and the unexposed portion are dissolved. Find each speed.

In the present invention, a polyimide precursor whose reaction to the final product is promoted by the action of the base is used, and when the reaction temperature of the polyimide precursor to the final product by the action of the base is not affected by the base, A polyimide precursor that is lower than that is used.
As the polyimide precursor used in the present invention, a polyimide precursor having a repeating unit represented by the following chemical formula (3) is preferably used.

(In Formula (3), R ³¹ is a tetravalent organic group. R ³² is a divalent organic group. R ³³ and R ³⁴ are a hydrogen atom or an organic group. N is 1 or more. It is a natural number.)

Examples of the case where R ³³ and R ³⁴ are organic groups are represented by an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _n H _2n OC _m H _{2m + 1} containing an ether bond therein. The structure etc. can be mentioned.

  As the polyimide precursor, a polyamic acid represented by the following formula (4) is preferably used from the viewpoint of alkali developability.

(In Formula (4), R ³¹ is a tetravalent organic group. R ³² is a divalent organic group. N is a natural number of 1 or more.)

In formulas (3) and (4), the tetravalent R ³¹ represents a tetracarboxylic acid residue derived from an acid dianhydride or the like, and the divalent R ³² represents a diamine residue. Incidentally, tetravalent R ³¹ represents only valence for bonding with the acid, but may have further substituents other. Similarly, the divalent value of R ³² indicates only the valence for bonding with the amine, but may have other substituents.

  Polyamic acid is preferable because it can be obtained by simply mixing acid dianhydride and diamine in a solution, so that it can be synthesized by a one-step reaction, and can be synthesized easily and at low cost.

  As a secondary effect, when the polyimide precursor to be used is a polyamic acid, it is sufficient that the temperature required for imidization is low due to the catalytic effect of the base. Can be lowered to In order to imidize the conventional polyamic acid, the final cure temperature had to be 300 ° C. or higher, so the use was limited. However, it became possible to lower the final cure temperature, so a wider range Applicable to usage.

Polyamic acid is obtained by the reaction of acid dianhydride and diamine. From the viewpoint of imparting excellent heat resistance and dimensional stability to the finally obtained polyimide, in the chemical formula (4), R ³¹ or R ^{32 is used.} Is preferably an aromatic compound, and R ³¹ and R ³² are more preferably aromatic compounds. At this time, in R ³¹ of the chemical formula (4), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ³¹ may be bonded to the same aromatic ring. May be bonded to different aromatic rings. Similarly, in R ³² of the chemical formula (4), two groups ((—NH—) ₂ ) bonded to R ³² may be bonded to the same aromatic ring or bonded to different aromatic rings. You may do it.

  The polyamic acid represented by the chemical formula (4) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.

  As a method for producing the polyimide precursor of the present invention, a conventionally known method can be applied. For example, (1) A method of synthesizing a polyamic acid as a precursor from an acid dianhydride and a diamine. (2) A polyimide precursor is synthesized by reacting a carboxylic acid such as an ester acid or an amic acid monomer with a monohydric alcohol, an amino compound, or an epoxy compound synthesized with an acid dianhydride. However, the method is not limited to this.

  Examples of the acid dianhydride applicable to the reaction for obtaining the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane. Aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarboxylic acid Anhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-di Carboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride, , 3-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [ 4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride,

2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarbo Cis) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) Phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetraca Boronic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic Acid dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride , Aromatic tetra such as m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride Examples thereof include carboxylic dianhydrides. These may be used alone or in combination of two or more. And as a particularly preferred tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  When acid dianhydride into which fluorine is introduced or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.

On the other hand, the amine component can also be used alone or in combination of two or more diamines. The diamine component used is not limited, p-phenylenediamine,
m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl Sulfide, 4,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4 ′ -Diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2 , 2-Di (4-aminophenyl) propa 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2, 2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1, 3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-amino Phenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3 -Aminophenoxy) benzene, 1,4- (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1, 4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1 , 4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α -Ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylben) L) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) Pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4 -Aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzen) ) Phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4 , 4′-Dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) -3,3 Such as 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, etc. Aromatic amines;

  1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω -Bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [ 2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane Ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12 -Aliphatic amines such as diaminododecane;

  1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4 -Di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] Alicyclic diamines such as heptane. Examples of guanamines include acetoguanamine, benzoguanamine, and the like, and some or all of the hydrogen atoms on the aromatic ring of the diamine are fluoro group, methyl group, methoxy group, trifluoromethyl group, or trifluoromethoxy group. Diamines substituted with substituents selected from the group can also be used.

  Further, depending on the purpose, any one or two or more of ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanato group, and isopropenyl group serving as a crosslinking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

  The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient. Rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like can be mentioned.

  In addition, diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring, for example, There exists what is represented by following formula (5). Specific examples include benzidine and the like.

(In the chemical formula (5), a is a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.)

Furthermore, in the above formula (5), a diamine having a substituent at a position where the amino group on the benzene ring is not substituted and which does not participate in the bond with another benzene ring can also be used. These substituents are organic groups, but they may be bonded to each other.
Specific examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino. Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl and the like can be mentioned.

  When the finally obtained polyimide is used as an optical waveguide or an optical circuit component, the transmittance for electromagnetic waves having a wavelength of 1 μm or less can be improved by introducing fluorine as a substituent of the aromatic ring.

On the other hand, when a diamine having a siloxane skeleton such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane is used as the diamine, the elastic modulus of the finally obtained polyimide is lowered and the glass transition temperature is lowered. be able to.
Here, the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance. However, depending on the desired physical properties, the diamine may be an aliphatic diamine or siloxane within a range not exceeding 60 mol%, preferably not exceeding 40 mol%. Non-aromatic diamines such as diamines may be used.

On the other hand, in order to synthesize a polyimide precursor, for example, while cooling a solution in which 4,4′-diaminodiphenyl ether as an amine component is dissolved in an organic polar solvent such as N-methylpyrrolidone, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is gradually added and stirred to obtain a polyimide precursor solution.
The polyimide precursor synthesized in this way has a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide obtained is required to have heat resistance and dimensional stability. Is preferred. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure The proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and particularly preferably a wholly aromatic polyimide.

In the polyimide precursor used in the present invention, in order to increase the sensitivity when a photosensitive polyimide resin composition is used and to obtain a pattern shape that accurately reproduces the mask pattern, the exposure wavelength is adjusted to a film thickness of 1 μm. On the other hand, it is preferable that the transmittance is at least 5% or more, and it is more preferable that the transmittance is 15% or more.
The high transmittance of the polyimide precursor with respect to the exposure wavelength means that there is little loss of electromagnetic waves, and a highly sensitive photosensitive polyimide resin composition can be obtained.

  In addition, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a transmittance with respect to an electromagnetic wave having a wavelength of at least 436 nm, 405 nm, and 365 nm is formed on a film having a thickness of 1 μm. Is preferably 5% or more, more preferably 15%, particularly preferably 50% or more.

  The weight average molecular weight of the polyimide precursor used in the present invention is preferably in the range of 3,000 to 1,000,000, and preferably in the range of 5,000 to 500,000, although it depends on the application. Is more preferable, and the range of 10,000 to 500,000 is more preferable. When the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when heat treatment or the like is performed to obtain a polymer such as polyimide. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases, the solubility tends to decrease, and it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.

  The molecular weight used here refers to a value in terms of polystyrene by gel permeation chromatography (GPC), may be the molecular weight of the polyimide precursor itself, or after chemical imidization treatment with acetic anhydride or the like. Things can be used.

  The solvent for the synthesis of the polyimide precursor is preferably a polar solvent, and representative examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl. Acetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethylphosphoamide, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, There are cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like, and these solvents are used alone or in combination of two or more. In addition to these, non-polar solvents such as benzene, benzonitrile, 1,4-dioxane, tetrahydrofuran, butyrolactone, xylene, toluene, cyclohexanone, and the like can be used as a solvent. It is used as a reaction regulator, a volatilization regulator of a solvent from the product, a film smoothing agent, and the like.

(Photobase generator)
The photobase generator used in the negative photosensitive polyimide resin composition according to the present invention can be the same as the photobase generator according to the present invention. Especially, it is preferable that the base which a photobase generator generate | occur | produces is a base which melt | dissolves the said polyimide precursor 10 weight part or more with respect to 100 weight part of the said base in any temperature of 150-200 degreeC. When the generated base dissolves 10 parts by weight or more of the polyimide precursor, the affinity between the catalyst base and the polyimide precursor is improved, and the polyimide precursor is efficiently imidized even with a small amount of base. Because it can.

  The photobase generator according to the present invention can be cured with a small amount of addition, and is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the entire solid content of the photosensitive polyimide resin composition. It is preferable to make it contain in the range of%. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a monomer that is liquid at room temperature.

<Other ingredients>
The photosensitive polyimide resin composition according to the present invention may be a simple mixture of the polyimide precursor, the photobase generator, and a solvent, but further, other than the light or thermosetting component and the polyimide precursor. A non-polymerizable binder resin and other components may be blended to prepare a photosensitive polyimide resin composition. Moreover, you may add the other photosensitive component which generate | occur | produces an acid or a base by light as an auxiliary role of the photobase generator of this invention. Further, a base proliferating agent that generates a base by decomposition or rearrangement reaction by the action of a small amount of base generated from the photobase generator may be used in combination, or a sensitizer may be added.

  Various general-purpose solvents can be used as a solvent for dissolving, dispersing, or diluting the photosensitive polyimide resin composition. Moreover, when using polyamic acid as a precursor, you may use the solution obtained by the synthesis reaction of polyamic acid as it is, and may mix other components there as needed.

  Examples of general-purpose solvents that can be used include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene glycol mono Glycol monoethers (so-called cellosolves) such as ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), propylene Esters such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o- Halogenated hydrocarbons such as chlorobenzene and m-dichlorobenzene; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide and the like Amides of N; pyrrolidones such as N-methyl-2-pyrrolidone and N-acetyl-2-pyrrolidone; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, dimethyl sulfone, Examples include sulfones such as tetramethylene sulfone and dimethyltetramethylene sulfone, phosphoric acid amides such as hexamethylphosphoamide, and other organic polar solvents, and aromatics such as benzene, toluene, xylene, and pyridine. Hydrocarbons and their Other organic nonpolar solvents are also included. These solvents are used alone or in combination.

  Among them, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene, etc. Aromatic hydrocarbons and mixed solvents composed of these solvents are preferred.

  As the photocurable component, a compound having one or more ethylenically unsaturated bonds can be used. For example, an amide monomer, a (meth) acrylate monomer, a urethane (meth) acrylate oligomer, a polyester (meth) Aromatic vinyl compounds such as acrylate oligomers, epoxy (meth) acrylates, hydroxyl group-containing (meth) acrylates, and styrene can be exemplified. In addition, when the polyimide precursor has a carboxylic acid component such as polyamic acid in the structure, the use of an ethylenically unsaturated bond-containing compound having a tertiary amino group causes the carboxylic acid of the polyimide precursor to have an ionic bond. When the photosensitive polyimide resin composition is formed, the dissolution rate contrast of the exposed and unexposed areas is increased.

  When using a photocurable compound having such an ethylenically unsaturated bond, a photoradical generator may be further added. Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethyl Thioxanthone such as luthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Monoacylphosphine oxides or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones.

  Examples of the compound that generates an acid by light include a photosensitive diazoquinone compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. US Pat. Nos. 2,772,972, 2,797, No. 213, No. 3,669,658. In addition, known photoacid generators such as triazine and derivatives thereof, sulfonic acid oxime ester compounds, sulfonic acid iodonium salts, and sulfonic acid sulfonium salts can be used. Examples of the compound that generates a base by light include 2,6-dimethyl-3,5-dicyano-4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl. Examples include -4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. it can.

Examples of the base proliferating agent include a compound having 9-fluorenylmethyl carbamate bond, 1,1-dimethyl-2-cyanomethyl carbamate bond ((CN) CH ₂ C (CH ₃ ) ₂ OC (O) NR ₂ ), Compounds having a paranitrobenzyl carbamate bond, compounds having a 2,4-dichlorobenzyl carbamate bond, and other urethane compounds described in paragraphs 0010 to 0032 of JP 2000-330270 A And urethane compounds described in paragraphs 0033 to 0060 of JP-A-2008-250111.

The addition of a sensitizer may be effective when it is desired to make the photobase generator sufficiently use the energy of the electromagnetic wave having a wavelength that transmits the polymer to improve the sensitivity.
In particular, when the absorption of the polyimide precursor is also at a wavelength of 360 nm or more, the effect of adding a sensitizer is great. Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, coumarins and derivatives thereof, ketocoumarin and derivatives thereof, ketobiscoumarin and derivatives thereof, cyclopentanone and derivatives thereof , Cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, thioxanthene series, xanthene series and derivatives thereof.

Specific examples of coumarin, ketocoumarin and derivatives thereof include 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin). ) And the like. Specific examples of thioxanthone and derivatives thereof include diethyl thioxanthone and isopropyl thioxanthone. Furthermore, benzophenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1,2-benzanthraquinone, 1,2-naphthoquinone, etc. Is mentioned.
Since these exhibit a particularly excellent effect in combination with a photobase generator, a sensitizer exhibiting an optimal sensitizing action is appropriately selected depending on the structure of the base generator.

  In addition, various organic or inorganic low-molecular or high-molecular compounds may be blended to impart processing characteristics and various functionalities to the resin composition according to the present invention. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

  Moreover, the mixture ratio of arbitrary components other than a solvent has the preferable range of 0.1 to 95 weight% with respect to the whole solid content of the photosensitive polyimide resin composition. When the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when it exceeds 95% by weight, the properties of the finally obtained resin cured product are not easily reflected in the final product.

  The photosensitive polyimide resin composition according to the present invention uses a resin material such as printing ink, paint, sealant, adhesive, electronic material, optical circuit component, molding material, resist material, building material, stereolithography, optical member, etc. It can be used for all known fields and products. It can be suitably used both for applications that are used by exposing the entire surface, such as paints, sealants, and adhesives, and for applications that form patterns such as permanent films and release films.

  The photosensitive polyimide resin composition according to the present invention can be used in a wide range of fields, products such as paints, printing inks, sealants, or adhesives, in which properties such as heat resistance, dimensional stability, and insulation are effective. , Display devices, semiconductor devices, electronic components, micro electro mechanical systems (MEMS), optically shaped objects, optical members, or building materials. For example, specifically, as a forming material for an electronic component, a sealing material and a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring covering film, and the like. Moreover, as a forming material of a display device, a layer forming material or an image forming material can be used for a color filter, a film for flexible display, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, a resist material, a layer forming material such as a buffer coat film, or the like can be used. Further, as a material for forming an optical component, it can be used as an optical material or a layer forming material for a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, or the like. Moreover, as a building material, it can use for a coating material, a coating agent, etc. It can also be used as a material for an optically shaped object.

  Since it has the above characteristics, the photosensitive polyimide resin composition according to the present invention can also be used as a pattern forming material. In particular, when the photosensitive polyimide resin composition is used as a pattern forming material (resist), the pattern formed thereby functions as a component that imparts heat resistance and insulation as a permanent film made of polyimide, for example, Suitable for forming color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, and other optical or electronic members.

  In the present invention, the printed material, paint, sealant, adhesive, display device, semiconductor device, electronic device, at least part of which is formed of the negative photosensitive polyimide resin composition according to the present invention or its thermoset. Articles of any of parts, microelectromechanical systems, stereolithography, optical members or building materials are provided.

<Relief pattern manufacturing method>
The method for producing a relief pattern according to the present invention comprises forming a coating film or a molded body comprising the negative photosensitive polyimide resin composition according to the present invention, and irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern. Then, after the irradiation or heating at the same time as the irradiation, the solubility of the irradiated portion is changed and then developed.

  In the manufacturing method of the relief pattern, the surface of the coating film or molded body made of the photosensitive polyimide resin composition is protected from the developer by using the polyimide precursor and the photobase generator according to the present invention in combination. Therefore, it is possible to form a pattern for development without using a resist film.

  A coating film is formed by coating the photosensitive polyimide resin composition according to the present invention on some support, or a molded body is formed by a suitable molding method, and the coating film or molded body is formed into a predetermined pattern. The photobase generator according to the present invention generates a base only in the exposed area by irradiating electromagnetic waves in a shape and heating after irradiation or simultaneously with irradiation. The base acts as a catalyst for promoting imidation of the polyimide precursor in the exposed portion. By using the photobase generator of the present invention, the heating conditions can be relaxed more than before, and imidation of the unexposed part of the photosensitive polyimide resin composition can be suppressed more than before, so the development time is shortened. In addition, a basic aqueous solution to which no alcohol or the like is added can be used as a developer, and the solubility contrast between the exposed portion and the unexposed portion can be increased.

The polyimide precursor has a lower thermosetting temperature due to the catalytic action of the base. In such a case, first, the part which wants to leave the pattern on the coating film or molded object of the photosensitive polyimide resin composition which concerns on this invention is exposed. When heated after exposure or simultaneously with exposure, a base is generated in the exposed area, and the thermosetting temperature of that area is selectively lowered. After the exposure or simultaneously with the exposure, the exposed portion is heat-cured but the unexposed portion is heated at a processing temperature that is not heat-cured, and only the exposed portion is cured. The heating step for generating the base and the heating step (post-exposure baking) for performing the reaction for curing only the exposed portion may be the same step or different steps.
Next, the unexposed portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  The photosensitive polyimide resin composition of the present invention comprises propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ- After dissolving in polar solvents such as butyrolactone, aromatic hydrocarbons such as toluene, and mixed solvents composed of these solvents, dipping, spraying, flexographic printing, gravure printing, screen printing, spin coating, Apply to the surface of the substrate such as silicon wafer, metal substrate, ceramic substrate, resin film, etc. by dispensing method and heat to remove most of the solvent to give a non-sticky coating on the substrate surface Can do. Although there is no restriction | limiting in particular in the thickness of a coating film, it is preferable that it is 0.5-50 micrometers, and it is more desirable that it is 1.0-20 micrometers from a sensitivity and a development speed surface. As drying conditions of the apply | coated coating film, 80-100 degreeC and 1 minute-20 minutes are mentioned, for example.

  This coating film is irradiated with electromagnetic waves through a mask having a predetermined pattern, and is exposed to a pattern. After heating, the unexposed portion of the film is developed and removed with an appropriate developer to obtain a desired pattern. A patterned film can be obtained.

  The exposure method and the exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure. A contact / proximity exposure machine using a g-line stepper, i-line stepper, ultrahigh pressure mercury lamp, or mirror projection exposure machine. Alternatively, a projector or a radiation source that can irradiate ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

  For example, when a protective group such as a photobase generator represented by the above formula (1-1) is present and the protective group is deprotected only by electromagnetic wave irradiation, it is removed by the electromagnetic wave irradiated to generate a base. The wavelength may be changed between an electromagnetic wave for deprotection and an electromagnetic wave for generating a base. For example, deprotection is performed by irradiating a long wavelength electromagnetic wave, and then isomerization is performed to generate a base with a short wavelength electromagnetic wave. The irradiation amount of the electromagnetic wave in these cases varies depending on the electromagnetic wave and is not particularly limited, and is appropriately adjusted.

The heating temperature for heating before exposure or after exposure or simultaneously with exposure to deprotect the protecting group to generate a base is appropriately selected depending on the polyimide precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the photosensitive polyimide resin composition is placed may be used, and in that case, a base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. The heating temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher, from the viewpoint of increasing the reaction rate and generating base efficiently. It is. However, depending on the polyimide precursor used in combination, for example, an unexposed portion may be cured by heating at 60 ° C. or higher, so that a suitable heating temperature is not limited to the above. Moreover, in order to prevent decomposition other than base generation of the photobase generator according to the present invention, heating at 300 ° C. or lower is preferable, and heating at 200 ° C. or lower is more preferable.
In addition, for example, when it has a protecting group such as a photobase generator represented by the above formula (1-1), it may be deprotected by heating before exposure. Depending on the type of the protecting group or the like, the sensitivity of the photobase generator may be deteriorated by introducing a protecting group or the like to shorten the absorption wavelength. In such a case, the sensitivity at the time of electromagnetic wave irradiation can be improved by deprotecting a protective group or the like in advance by heating before the electromagnetic wave irradiation and irradiating the electromagnetic wave.
The deprotection conditions for the protecting group can vary depending on the components that coexist in the composition. For example, when other photoacid generators or photobase generators are included, the heating temperature after exposure may change due to the influence of an acid / base generated by light irradiation.
The heating for protecting group deprotection before the electromagnetic wave irradiation may be a coating film drying process or another heating process. In this case, as the heating temperature, a temperature capable of deprotection may be selected as appropriate, but it is preferably 50 ° C. to 180 ° C., and the time is preferably 10 seconds to 60 minutes.
In addition, when heating is performed, the protecting group may be deprotected at a low temperature to generate a base at a higher temperature.

  The photobase generator represented by the formula (1-1) generates a base only by irradiation with electromagnetic waves, but generation of the base is promoted by heating appropriately. Therefore, in order to efficiently generate a base, when using the photobase generator represented by the formula (1-1), the base is formed by heating after electromagnetic wave irradiation (exposure) or simultaneously with electromagnetic wave irradiation. Is generated. Exposure and heating may be performed alternately. The most efficient method is a method of heating simultaneously with exposure.

The coating film of the photosensitive polyimide resin composition according to the present invention is preferably subjected to a post exposure bake (PEB) between the exposure process and the development process in order to perform a reaction for curing only the exposed portion. . The PEB is carried out at a temperature at which the reaction rate of the curing reaction such as the imidization rate differs between the site where the base is present and the site where the base is not present without irradiation due to the action of the base generated by the electromagnetic wave irradiation It is preferable that it is appropriately selected depending on the type of photobase generator used. The range of the temperature of the preferable heat treatment is usually about 140 ° C to 210 ° C, more preferably 150 ° C to 200 ° C. If the heat treatment temperature is lower than 140 ° C., the imidization efficiency is poor, and it becomes difficult to cause a difference in the imidization ratio between the exposed and unexposed areas under realistic process conditions. On the other hand, when the heat treatment temperature exceeds 210 ° C., imidization may proceed even in an unexposed portion where no base is present, and it is difficult to cause a difference in solubility between the exposed portion and the unexposed portion.
Moreover, since the generated base is a liquid at least at a temperature of 150 to 200 ° C., it is particularly preferable to appropriately select the temperature at which the generated base becomes a liquid. When the generated base is a liquid, it is easy to diffuse in the resin composition, or the polyimide precursor in the resin composition can be dissolved, so the polyimide precursor can be efficiently used even with a small amount of base. This is because it can be imidized.
This heat treatment may be any method as long as it is a known method, and specific examples thereof include heating with a circulating oven in a nitrogen atmosphere or a hot plate, or the like, but is not particularly limited.

(Developer)
The developer used in the development step is not particularly limited as long as the solvent that changes the solubility of the irradiated site is used as the developer, and is appropriately selected according to the polyimide precursor to be used, such as a basic aqueous solution or an organic solvent. Is possible. From the viewpoint of reducing the burden on the environment, the developer preferably contains a small amount of organic solvent. Specifically, a basic aqueous solution having an organic solvent content of 20% by weight or less is preferred. A basic aqueous solution having a content of 10% by weight or less is more preferred. Ideally, a basic aqueous solution containing substantially no organic solvent such as alcohol is most preferable.

Although it does not specifically limit as basic aqueous solution, For example, other than tetramethylammonium hydroxide (TMAH) aqueous solution whose density | concentration is 0.01 weight%-10 weight%, Preferably, 0.05 weight%-5 weight%. , Diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl Examples of the aqueous solution include methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and tetramethylammonium.
The solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.

  The organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, Alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, other tetrahydrofuran, chloroform, acetonitrile and the like alone or Two or more types may be added in combination. After development, washing is performed with water or a poor solvent. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.

  After development, if necessary, rinse with water or a poor solvent and dry at 80 to 100 ° C. to stabilize the pattern. In order to make this relief pattern heat resistant, a patterned high heat resistant resin layer is formed by heating at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several tens of minutes to several hours. The

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified. The structure of the produced base generator was confirmed by ¹ H NMR.
¹ H NMR measurement: JEOL JNM-LA400WB, manufactured by JEOL Ltd.
Manual exposure machine: manufactured by Dainippon Kaken, MA-1100
Absorbance measurement: UV-2550 manufactured by Shimadzu Corporation, UV-visible spectrophotometer
Heating of coating film: manufactured by ASONE Co., Ltd., HOT PLATE EC-1200 (may be described as hot plate in this example)

(Synthesis Example 1: Synthesis of polyimide precursor 1)
20.0 g (100 mmol) of 4,4′-diaminodiphenyl ether (ODA) was put into a 500 ml separable flask and dissolved in 181 g of dehydrated N-methyl-2-pyrrolidone (NMP) under an nitrogen stream under an oil bath. The mixture was monitored with a thermocouple so that the liquid temperature became 50 ° C. and stirred while heating. After confirming that they were completely dissolved, 2,3 g (93.1 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added thereto gradually over 30 minutes. After the addition, the mixture was stirred at 50 ° C. for 5 hours. Thereafter, 0.900 g (6.08 mmol) of phthalic anhydride was added. Then, it cooled to room temperature and obtained the polyimide precursor 1 solution which has a repeating unit represented by a following formula.

(Synthesis Example 2: Synthesis of polyimide precursor 2)
16.0 g (50.0 mmol) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFMB) and 2,2′-dimethyl-4,4′-diaminobiphenyl (mTBHG) 10. 6 g (50.0 mmol) is put into a 500 ml separable flask, dissolved in 200 g of dehydrated N-methyl-2-pyrrolidone (NMP), and the liquid temperature is 50 ° C. by an oil bath under a nitrogen stream. The mixture was monitored with a thermocouple and stirred while heating. After confirming that they were completely dissolved, 2,3 g (93.1 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was gradually added thereto over 30 minutes. After the addition, the mixture was stirred at 50 ° C. for 5 hours. Thereafter, 0.900 g (6.08 mmol) of phthalic anhydride was added. Then, it cooled to room temperature and obtained the polyimide precursor 2 solution which has a repeating unit represented by a following formula.

(Synthesis Example 3: Synthesis of polyimide precursor 3)
Into a 1000 ml separable flask under nitrogen flow, 85.5 g of dehydrated N-methyl-2-pyrrolidone (NMP) is charged and monitored with a thermocouple so that the liquid temperature becomes 50 ° C. by an oil bath and heated. While stirring. 13.0 g (44.2 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added, and then 1,3-bis (3-aminopropyl) tetramethyldisiloxane 5 .14 g (20.7 mmol) was added. After confirming dissolution after 60 minutes, 401.7 g of dehydrated N-methyl-2-pyrrolidone (NMP) was added, and 37.3 g (186 mmol) of 4,4′-diaminodiphenyl ether (ODA) was dissolved.
After confirming that they were completely dissolved, 4,6.7 g (159 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added and stirred at 50 ° C. for 5 hours. Thereafter, 0.994 g (6.71 mmol) of phthalic anhydride was added, and the mixture was stirred at 50 ° C. for 1 hour and end-capped. Then, it cooled to room temperature and obtained the polyimide precursor 3 solution which has a repeating unit represented by a following formula. (R in the formula is an organic group represented by R1 or R2, and the ratio of R1 and R2 is R1: R2 = 90: 10.)

[Test Example: Evaluation 1 of catalytic ability of each base]
The catalytic ability to promote imidization of the base generated from the photobase generator according to the present invention was evaluated.
(1) Preparation of polyimide precursor resin composition solution and preparation of coating film To the polyimide precursor 1 solution obtained in Synthesis Example 1, the bases listed in Table 1 were added to the solid content of the polyimide precursor 1 solution. It is added at a rate of 0.6 mmol per 1 g, and polyimide precursor resins of Test Examples 2, 6-11, 14-15, Reference Test Examples 1, 3-5, 12, 13 and Comparative Test Examples 1-8 A composition solution was prepared.
In addition, a sample obtained by adding 0.6 mmol of piperidine and cyclohexanol to the polyimide precursor 1 solution obtained in Synthesis Example 1 with respect to 1 g of the solid content of the polyimide precursor 1 solution was compared with that of Comparative Test Example 9. The polyimide precursor resin composition solution was used, and the polyimide precursor 1 solution itself was used as a blank as the polyimide precursor resin composition solution of Comparative Test Example 10. Moreover, when a polyimide precursor resin composition solution was prepared in the same manner as in Reference Test Example 1 using isonipecotic acid as a base, since isonipecotic acid was not dissolved in the polyimide precursor 1 solution, the imidization rate was measured. could not.
Each polyimide precursor resin composition solution obtained was spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 11 ± 1 μm after drying, and then dried on a hot plate at 100 ° C. for 15 minutes. A corresponding coating was prepared.

  From the results in Table 1, it can be seen that a base having a hydroxyl group having a boiling point of 150 ° C. or higher and a melting point of 200 ° C. or lower has a high catalytic ability to improve the imidization rate of the polyimide precursor.

[Test example: Evaluation of catalytic ability of each base 2]
The base having a hydroxyl group having a boiling point of 150 ° C. or higher and a melting point of 200 ° C. or lower, which was evaluated as having high catalytic ability in the evaluation 1 of the catalytic ability of each of the above bases in the polyimide precursor 1 solution obtained in Synthesis Example 1 4-piperidinemethanol was added at a ratio shown in Table 2 with respect to 1 g of the solid content of the polyimide precursor 1 solution, and the polyimide precursor resin composition solution of Test Example 16 was prepared at four concentrations.
Further, in Test Example 16, the same procedure as in Test Example 16 was used except that 4-hydroxypiperidine, which is a base having a hydroxyl group having a boiling point of 150 ° C. or higher and a melting point of 200 ° C. or lower, was used instead of 4-piperidinemethanol. The polyimide precursor resin composition solution of Test Example 17 was prepared at four concentrations.
Further, in Test Example 16, the polyimide precursor resin composition solution of Comparative Test Example 11 was prepared in four concentrations in the same manner as in Test Example 16 except that piperidine having no hydroxyl group was used instead of 4-piperidinemethanol. It was prepared with.

The obtained polyimide precursor resin composition solutions of each concentration in Test Examples 16 to 17 and Comparative Test Example 11 were spin-coated on chrome-plated glass (50 mm × 50 mm), respectively, so as to be 11 ± 1 μm after drying. And it was made to dry for 15 minutes on a 100 degreeC hotplate, and each corresponding coating film was produced.
Each coating film was heated on a hot plate at 160 ° C. for 10 minutes. The imidation ratio of each coating film at that time was determined from the IR spectrum in the same manner as in the evaluation 1 of the catalytic ability of each base.
The relationship between the addition amount (mmol / g) of each base with respect to 1 g of the solid content of the polyimide precursor 1 solution and the imidization ratio is shown in FIG.

  From the results of FIG. 1, it was revealed that the coating film added with 4-piperidinemethanol and 4-hydroxypiperidine can achieve a high imidization ratio even with a small addition amount compared to the coating film added with piperidine. This shows that a base having a hydroxyl group having a boiling point of 150 ° C. or higher and a melting point of 200 ° C. or lower has high catalytic ability and can sufficiently promote imidization of the polyimide precursor with a small addition amount.

(Production Example 1: Synthesis of photobase generator 1)
In a 100 mL flask, 2.00 g of potassium carbonate was added to 15 mL of methanol. In a 50 mL flask, 2.67 g (6.2 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 945 mg of 2-hydroxy-4-methoxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.2 mmol) was dissolved in 10 mL of methanol and slowly added dropwise to a well-stirred potassium carbonate solution. After stirring for 3 hours, the completion of the reaction was confirmed by TLC, followed by filtration to remove potassium carbonate and concentration under reduced pressure. After concentration, 50 mL of 1N aqueous sodium hydroxide solution was added and stirred for 1 hour. After completion of the reaction, triphenylphosphine oxide was removed by filtration, and then concentrated hydrochloric acid was added dropwise to acidify the reaction solution. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 1.00 g of 2-hydroxy-4-methoxycinnamic acid. Subsequently, 1.00 g (5.1 mmol) of 2-hydroxy-4-methoxycinnamic acid was dissolved in 10 mL of dehydrated tetrahydroxyfuran in a 100 mL flask, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved. 1.18 g (6.2 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, 712 mg (6.2 mmol) of 4-piperidinemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with chloroform, the mixture was washed with 1N hydrochloric acid and saturated brine. Then, 100 mg of photobase generator 1 of Production Example 1 represented by the following formula was obtained by purification by silica gel column chromatography (developing solvent: chloroform / methanol = 100/1 to 10/1, volume ratio). .

(Production Example 2: Synthesis of photobase generator)
In Production Example 1, 625 mg (6.2 mmol) of 4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 712 mg (6.2 mmol) of 4-piperidine methanol (manufactured by Tokyo Chemical Industry Co., Ltd.). Otherwise, 83 mg of the photobase generator 2 of Production Example 2 represented by the following formula was obtained in the same manner as Production Example 1.

(Comparative Production Example 1: Synthesis of Comparative Photobase Generator 1)
In Example 1, instead of 712 mg (6.2 mmol) of 4-piperidinemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.61 ml (6.2 mmol) of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. In the same manner as in Production Example 1, 128 mg of Comparative Photobase Generator 1 of Comparative Production Example 1 represented by the following formula was obtained.

[Evaluation: Base generation ability of photobase generator]
Three 1 mg samples of each of the photobase generators obtained in Production Examples 1 and 2 and Comparative Production Example 1 were prepared, and each was dissolved in deuterated acetonitrile in a quartz NMR tube. Using a filter that transmits 20% of i-line and a high-pressure mercury lamp, one was irradiated with light at 400 mJ / cm ² , and the other was irradiated with light at 800 mJ / cm ² . The remaining one was not irradiated with light. ¹ H NMR of each sample was measured to determine the isomerization ratio.

The photobase generators obtained in Production Examples 1 and 2 and Comparative Production Example 1 were isomerized by irradiation at 400 mJ / cm ² and irradiation at 800 mJ / cm ² . When the isomerized sample was heated to 160 ° C., almost 100% of the isomerized compound was cyclized, and a base was generated along with it, resulting in the base generation rate (%) shown in Table 3.

(Example 1: Preparation of photosensitive polyimide resin composition 1)
15 parts by weight of the photobase generator 1 obtained in Production Example 1 is added to 100 parts by weight of the solid content of the polyimide precursor 2 solution obtained in Synthesis Example 2, and the photosensitive polyimide resin composition of Example 1 is added. 1 was prepared.
The base (4-piperidinemethanol) generated from the photobase generator 1 is 10 parts by weight of the polyimide precursor (solid content) obtained in Synthesis Example 2 with respect to 100 parts by weight of the base at 160 ° C. This was dissolved.

(Example 2: Preparation of photosensitive polyimide resin composition 2)
In Example 1, in place of the photobase generator 1 obtained in Production Example 1, the photobase generator 2 obtained in Production Example 2 was used, and the same procedure as in Example 1 was repeated. Photosensitive polyimide resin composition 2 was prepared.
The base (4-hydroxypiperidine) generated from the photobase generator 2 is 165 ° C. and 10 parts by weight of the polyimide precursor (solid content) obtained in Synthesis Example 2 with respect to 100 parts by weight of the base. This was dissolved.

(Example 3: Preparation of photosensitive polyimide resin composition 3)
22.3 parts by weight of the photobase generator 1 obtained in Production Example 1 is added to 100 parts by weight of the solid content of the polyimide precursor 1 solution obtained in Synthesis Example 1, and the photosensitive polyimide resin of Example 3 is added. Composition 3 was prepared.
In addition, the base (4-piperidinemethanol) generated from the photobase generator 1 is 10 parts by weight of the polyimide precursor (solid content) obtained in Synthesis Example 1 with respect to 100 parts by weight of the base at 160 ° C. This was dissolved.

(Example 4: Preparation of photosensitive polyimide resin composition 4)
22.3 parts by weight of the photobase generator 1 obtained in Production Example 1 is added to 100 parts by weight of the solid content of the polyimide precursor 3 solution obtained in Synthesis Example 3, and the photosensitive polyimide resin of Example 4 is added. Composition 4 was prepared.
The base (4-piperidinemethanol) generated from the photobase generator 1 is 10 parts by weight of the polyimide precursor (solid content) obtained in Synthesis Example 3 with respect to 100 parts by weight of the base at 160 ° C. This was dissolved.

(Comparative Example 1: Preparation of comparative photosensitive polyimide resin composition 1)
In the same manner as in Example 1 except that the comparative photobase generator 1 obtained in Comparative Production Example 1 was used in place of the photobase generator obtained in Production Example 1 in Example 1, Comparative Example 1 A comparative photosensitive polyimide resin composition 1 was prepared.
In addition, since the base (piperidine) generated from the comparative photobase generator 1 has a boiling point of 106 ° C., it cannot be attempted to dissolve the polyimide precursor in the base at any temperature of 150 ° C. to 200 ° C. It was.

(Comparative Example 2: Preparation of comparative photosensitive polyimide resin composition 2)
20 parts by weight of the comparative photobase generator 1 obtained in Comparative Production Example 1 is added to 100 parts by weight of the solid content of the polyimide precursor 1 solution obtained in Synthesis Example 1, and the comparative photosensitive polyimide in Comparative Example 2 is added. Resin composition 2 was prepared.
In addition, since the base (piperidine) generated from the comparative photobase generator 1 has a boiling point of 106 ° C., it cannot be attempted to dissolve the polyimide precursor in the base at any temperature of 150 ° C. to 200 ° C. It was.

(Comparative Example 3: Preparation of comparative photosensitive polyimide resin composition 3)
20 parts by weight of the comparative photobase generator 1 obtained in Comparative Production Example 1 is added to 100 parts by weight of the solid content of the polyimide precursor 3 solution obtained in Synthesis Example 3, and the comparative photosensitive polyimide in Comparative Example 3 is added. Resin composition 3 was prepared.
In addition, since the base (piperidine) generated from the comparative photobase generator 1 has a boiling point of 106 ° C., it cannot be attempted to dissolve the polyimide precursor in the base at any temperature of 150 ° C. to 200 ° C. It was.

[Evaluation of Photosensitive Polyimide Resin Composition: Developability Evaluation 1]
(1) Preparation of coating film After drying the photosensitive polyimide resin compositions of Examples 1, 2 and Comparative Example 1 on chrome-plated glass (50 mm × 50 mm), respectively, 17 ± 1 μm is obtained. Were coated on a hot plate at 100 ° C. for 15 minutes, and two coating films of the photosensitive polyimide resin compositions of Example 1, Example 2 and Comparative Example 1 were produced as a set.
One of the coating films produced as described above was used as a coating film for evaluating the exposed portion, and ² J / cm ² exposure was performed with a high-pressure mercury lamp using a manual exposure machine. The remaining one sheet was not exposed as a coating film for evaluating the unexposed area. Thereafter, each coating film was heated for 10 minutes at a temperature (PEB temperature) shown in Tables 4 to 6 below with a hot plate to obtain a developability evaluation sample. In each of the developability evaluation samples, two sheets, one coating film for evaluating the exposed area and one coating film for evaluating the unexposed area, were used as a set.

(2) Evaluation of developability Each coating film was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 50 ° C, and the dissolution rate of the coating film after 600 seconds was measured. The evaluation results of the photosensitive polyimide resin compositions of Example 1, Example 2, and Comparative Example 1 were as shown in Tables 4 to 6, respectively.
As a method for evaluating developability, the amount of film reduction (dissolution rate) per time between the exposed portion and the unexposed portion of each coating film was calculated and compared. It can be evaluated that the higher the ratio of the dissolution rate of the coating film in the exposed area to the dissolution rate of the coating film in the unexposed area (solubility contrast), the higher the remaining film ratio.
The unexposed part of Comparative Example 1 was hardly dissolved in the developer and swollen, and after 1200 seconds, the coating film was peeled off from the glass.

As a result of the evaluation, it was found that Example 1 and Example 2 had higher solubility contrast values than Comparative Example 1 at any PEB temperature. The photosensitive polyimide resin compositions of Example 1 and Example 2 have a high residual film ratio in a shorter time even when a basic aqueous solution to which no organic solvent such as alcohol is added is used as a developer because of a reduction in environmental burden. It can be estimated that a pattern having a good shape can be formed. On the other hand, it was suggested that the photosensitive polyimide resin composition of Comparative Example 1 cannot obtain a good relief pattern when a basic aqueous solution to which no organic solvent such as alcohol is added is used as a developer.
In addition, from the above results, the photosensitive polyimide resin composition of the present invention can sufficiently promote imidization of the polyimide precursor even when the heating conditions during post-exposure baking are relaxed compared to the prior art, and further introduced into the base. It was suggested that dissolution of the unexposed area in the developer was promoted by the effect of the hydroxyl group. It is presumed that the base having a hydroxyl group functions as a substitute for the alcohol conventionally added to the developer and also functions as a dissolution accelerator for promoting the dissolution of the polyimide precursor.

[Evaluation of Photosensitive Polyimide Resin Composition: Developability Evaluation 2]
(1) Preparation of coating film The photosensitive polyimide resin compositions of Example 3 and Comparative Example 2 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 2 μm after drying, and 120 It dried for 15 minutes on the hotplate of (degreeC), and produced the coating film of the photosensitive polyimide resin composition of Example 3 and Comparative Example 2 as 2 sets, respectively.
One of the coating films prepared as described above was used as a coating film for evaluating the exposed portion, and was exposed to 500 mJ / cm ^{2 with} a high-pressure mercury lamp using a manual exposure machine. The remaining one sheet was not exposed as a coating film for evaluating the unexposed area. Thereafter, each coating film was heated on a hot plate at 160 ° C. for 2 minutes to obtain a developability evaluation sample. In each of the developability evaluation samples, two sheets, one coating film for evaluating the exposed area and one coating film for evaluating the unexposed area, were used as a set.

(2) Evaluation of developability Each coating film was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23 ° C, and the dissolution rate of the coating film was measured. The developability was evaluated by the same method as in the above developability evaluation 1.
The evaluation results of the photosensitive polyimide resin composition of Example 3 and Comparative Example 2 were as shown in Table 7, respectively.

  As a result of the evaluation, it was found that Example 3 had a faster dissolution rate in the unexposed area and a higher solubility contrast value than Comparative Example 2.

[Evaluation of Photosensitive Polyimide Resin Composition: Developability Evaluation 3]
(1) Preparation of coating film Each of the photosensitive polyimide resin compositions of Example 4 and Comparative Example 3 was spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 2 μm after drying, and 120 It dried for 15 minutes on the hotplate of (degreeC), and produced the coating film of the photosensitive polyimide resin composition of Example 4 and Comparative Example 3 as 2 sets, respectively.
One of the coating films prepared as described above was used as a coating film for evaluating the exposed portion, and was exposed to 500 mJ / cm ^{2 with} a high-pressure mercury lamp using a manual exposure machine. The remaining one sheet was not exposed as a coating film for evaluating the unexposed area. Thereafter, each coating film was heated on a hot plate at 160 ° C. for 2 minutes to obtain a developability evaluation sample. In each of the developability evaluation samples, two sheets, one coating film for evaluating the exposed area and one coating film for evaluating the unexposed area, were used as a set.

(2) Evaluation of developability Each coating film was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23 ° C, and the dissolution rate of the coating film was measured. The developability was evaluated by the same method as in the above developability evaluation 1.
The evaluation results of the photosensitive polyimide resin compositions of Example 4 and Comparative Example 3 were as shown in Table 8, respectively.

  As a result of the evaluation, it was found that Example 4 had a higher dissolution rate in the unexposed area and a higher solubility contrast value than Comparative Example 3.

  From the results of developability evaluations 2-3, the photobase generator of the present invention sufficiently promotes imidization of the exposed area even when the composition of the polyimide precursor to be added is changed, while the unexposed area generates a base. It was suggested that a pattern having a good shape with a high residual film rate can be formed in a shorter time since the dissolution in the developer is promoted by the effect of the hydroxyl group introduced into the agent.

[Evaluation of photosensitive polyimide resin composition: Evaluation of coating film sensitivity and γ value 1]
The photosensitive polyimide resin compositions of Example 1, Example 2, and Comparative Example 1 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 18 ± 1 μm after drying, and 100 ° C. Each of the coating films was obtained by drying on a hot plate for 15 minutes.

The prepared coating film was exposed on the whole surface with a high-pressure mercury lamp using a manual exposure machine. For the coating film of Example 1, the entire surface was exposed at 0, 25, 50, 75, 100, 150, 300, 400, 500, 1000 mJ / cm ² , and for the coating film of Example 2. , 0, 50, 75, 100, 200, 300, 500, and 1000 mJ / cm ² were respectively exposed to the entire surface. The entire surface of the coating film of Comparative Example 1 was exposed at 0, 25, 75, 100, 200, 300, 400, 500, and 1000 mJ / cm ² . Thereafter, each coating film was hotplate at 160 ° C. for the coating film of Example 1, 165 ° C. for the coating film of Example 2, and 165 ° C. for the coating film of Comparative Example 1. Each of these coatings was heated for 10 minutes, and each of these coatings was mixed with a 2.5% aqueous solution of tetramethylammonium hydroxide and isopropanol at a ratio of 8: 2 for the coating of Example 1 at 40 ° C. for 5 minutes. The coating film of Example 2 was developed at 30 ° C. for 10 minutes, and the coating film of Comparative Example 1 was developed at 40 ° C. for 6 minutes, and the remaining film thickness on the substrate was measured. The results are shown in Table 9. Further, FIG. 2 shows a sensitivity curve representing the relationship between the exposure amount and the normalized residual film rate. The normalized residual film ratio in the figure was (film thickness after development × 100) / (maximum film thickness after development).
The sensitivity in the table is the exposure amount when the normalized residual film ratio obtained from the sensitivity curve is about 1. The γ value in the table is an index representing contrast, and the larger the value, the higher the contrast and the larger the taper angle pattern. The γ value was determined by the following formula.
γ = 1 / {log (exposure amount when normalized residual film ratio is about 1) −log (exposure amount when normalized residual film ratio is 0)}
In Example 2 and Comparative Example 1, the exposure amount at which the normalized residual film ratio was 0 could not be accurately measured. Therefore, the exposure amount at which the normalized residual film ratio was the minimum (Example 2 was 50 mJ, Comparative Example). 1 was 25 mJ). The γ value was calculated as an exposure amount when the normalized residual film ratio was 0.

Since the residual film rate increases with the increase in the UV irradiation amount, the base generator generates a secondary amine having one NH group capable of forming an amide bond by UV irradiation and heating. Was shown to be in progress. In Example 1, 100 mJ / cm ² of the present invention, normalized residual film ratio was about 1 in Example 2 in 75 mJ / cm ^2. In contrast, in Comparative Example 1, the normalized residual film rate was about 1 at 100 mJ / cm ² . From this, it was shown that imidization progresses with the exposure amount comparable as the comparative photosensitive polyimide resin composition of the photosensitive polyimide resin composition of this invention.
On the other hand, the larger the γ value, the higher the solubility contrast and the larger the taper angle pattern. In Example 1 of the present invention, the γ value was 8.0, and in Example 2, the γ value was 5.4, whereas in Comparative Example 1, the γ value was 1.6. From this, it was shown that the photosensitive polyimide resin composition of this invention has a high solubility contrast compared with a comparative photosensitive polyimide resin composition, and can obtain the pattern of a shape close | similar to a rectangle.

[Evaluation of photosensitive polyimide resin composition: Evaluation of coating film sensitivity and γ value 2]
The photosensitive polyimide resin compositions of Example 3 and Comparative Example 2 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 2 μm after drying. Each coating film was obtained by drying for a few minutes.

  The prepared coating film was exposed to the entire surface with a high-pressure mercury lamp with an appropriate exposure amount selected using a manual exposure machine. Thereafter, each coating film was heated at 160 ° C. for 2 minutes by a hot plate. Each of these coating films was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 90 seconds for the coating film of Example 3 and 150 seconds for the coating film of Comparative Example 2. The remaining film thickness on the substrate was measured. The results are shown in Table 10. FIG. 3 shows a sensitivity curve representing the relationship between the exposure amount and the normalized residual film rate. In addition, the normalized residual film ratio in the figure, the sensitivity in the table, and the γ value are the same as in the evaluation 1 of the sensitivity and γ value of the coating film.

Since the residual film rate increases with the increase in the UV irradiation amount, the base generator generates a secondary amine having one NH group capable of forming an amide bond by UV irradiation and heating. Was shown to be in progress. In Example 3 of the present invention, the normalized residual film ratio was 1 at 118 mJ / cm ² and in Comparative Example 2 at 82 mJ / cm ² .
On the other hand, the larger the γ value, the higher the solubility contrast and the larger the taper angle pattern. In Example 3 of the present invention, the γ value was 1.8, while in Comparative Example 2, the γ value was 1.1. From this, it was shown that the photosensitive polyimide resin composition of this invention has a high solubility contrast compared with a comparative photosensitive polyimide resin composition, and can obtain the pattern of a shape close | similar to a rectangle.

[Evaluation of photosensitive polyimide resin composition: Pattern forming ability evaluation 1]
The photosensitive polyimide resin compositions of Example 1, Example 2, and Comparative Example 1 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 18 ± 1 μm after drying, and 100 ° C. Each of the coating films was obtained by drying on a hot plate for 15 minutes.

The prepared coating film was exposed to 200 mJ / cm ² through a fine line evaluation mask with a high-pressure mercury lamp using a manual exposure machine. Subsequently, the coating films of Example 2 and Comparative Example 1 were heated at 165 ° C. and the coating film of Example 1 at 160 ° C. for 5 minutes, respectively.
In order to reduce the burden on the environment, these samples were developed by using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide that does not contain alcohol. This was performed by immersing the sample in a state heated to ° C.
Usually, by removing alcohol from the developer, the environmental load is reduced, while the development speed of the unexposed area is lowered and the development time is lengthened.

  After the pattern formation, the coating film was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere (temperature rising rate: 10 ° C./min, natural cooling) and then cured. As a result, thin film patterns as shown in Table 11 were obtained for the coating films of Example 1 and Example 2. About the coating film of the comparative example 1, even if it immersed in the developing solution for 1 hour or more, the unexposed part remained and the pattern was not able to be formed. From this result, it became clear that the photosensitive polyimide resin composition of the present invention can form a good pattern.

<Evaluation criteria for pattern shape>
◎: The taper angle of the pattern cross section exceeds 55 degrees ○: The taper angle of the pattern cross section is 30 to 55 degrees

  In the case of the comparative photosensitive polyimide resin composition of Comparative Example 1, phenomena such as gelation or swelling of the unexposed portion were observed, and it was difficult to dissolve in the developer. On the other hand, when the generated base has a hydroxyl group as in the photosensitive polyimide resin compositions of Example 1 and Example 2, even when a highly water-repellent fluorine-containing polyimide precursor is used, as described above in the unexposed area. The phenomenon was not seen. This is presumably because the affinity of the unexposed area with the alkaline aqueous solution was improved by the effect of the hydroxyl group of the generated base. Further, when the photosensitive polyimide resin composition of Example 1 was used, the PEB temperature could be lowered to 160 ° C., so that imidization of the unexposed area could be suppressed and the development time could be shortened.

[Evaluation of photosensitive polyimide resin composition: Pattern forming ability evaluation 2]
The photosensitive polyimide resin compositions of Example 3 and Comparative Example 2 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 2 μm after drying. Each coating film was obtained by drying for a few minutes.
The prepared coating film was exposed to 200 mJ / cm ² through a fine line evaluation mask with a high-pressure mercury lamp using a manual exposure machine. Subsequently, each coating film was heated at 160 ° C. for 2 minutes.
The development of these samples was processed for 90 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide not containing alcohol in order to reduce the burden on the environment.
As a result, for the coating film of Example 3, formation of a fine line pattern having a post-development film thickness of 1.60 μm and a residual film ratio of 90% was confirmed.
On the other hand, with respect to the coating film of Comparative Example 2, an unexposed portion still remained in the development process for 90 seconds, and a pattern could not be formed.
From the result of pattern formation ability evaluation 2, it was revealed that the photosensitive polyimide resin composition of Example 3 can form a good pattern in a shorter time than Comparative Example 2.

[Evaluation of photosensitive polyimide resin composition: Pattern forming ability evaluation 3]
The photosensitive polyimide resin compositions of Example 4 and Comparative Example 3 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to have a thickness of 2 μm, and 15% on a 120 ° C. hot plate. Each coating film was obtained by drying for a few minutes.
The prepared coating film was exposed to 200 mJ / cm ² through a fine line evaluation mask with a high-pressure mercury lamp using a manual exposure machine. Subsequently, each coating film was heated at 160 ° C. for 2 minutes.
The development of these samples was processed for 60 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide not containing alcohol in order to reduce the burden on the environment.
As a result, for the coating film of Example 4, formation of a fine line pattern with a post-development film thickness of 1.48 μm and a residual film ratio of 81% was confirmed.
About the coating film of the comparative example 3, the unexposed part still remained by the development processing for 60 second, and the pattern was not able to be formed.
From the result of pattern formation ability evaluation 3, it was revealed that the photosensitive polyimide resin composition of Example 4 can form a good pattern in a short time as compared with Comparative Example 3.

  From the above results, the base having a hydroxyl group has a high catalytic ability for imidization, and the photosensitive polyimide resin composition of the present invention using the photobase generator that generates such a base is heated during post-exposure baking. Even if the conditions are relaxed from the conventional conditions, it is clear that imidization of the polyimide precursor can be sufficiently promoted, and further, the dissolution of the unexposed area in the developer is promoted by the effect of the hydroxyl group introduced into the base. It became. As a result, the photosensitive polyimide resin composition of the present invention can shorten the development time, and can use a basic aqueous solution to which no alcohol or the like is added as a developer. It has been clarified that an effect can be obtained that a pattern with higher resolution can be formed and the shape of the relief pattern is improved.

Claims (9)

A base generator represented by the following chemical formula (1-1) or the following chemical formula (1-2), wherein the generated base is latentized using a covalent bond and generates a base upon irradiation with electromagnetic waves, A photobase generator for a precursor type photosensitive polyimide, wherein the base to be used is a secondary amine having a hydroxyl group.
(In Formula (1-1), R ¹ and R ² are each independently an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And may contain a bond of hetero atoms, provided that any organic group of R ¹ and R ² has a hydroxyl group, and R ³ and R ⁴ each independently represents a hydrogen atom, A halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, may be different even in the same ^{.R 5, R 6,} R ⁷ and ^{R 8} each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol , Nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group or organic group, which may be the same or different. Two or more of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to form a cyclic structure, and may contain a hetero atom bond, R ⁹ may be a hydrogen atom, Alternatively, it is a protective group that can be removed by heating and / or irradiation with electromagnetic waves.)
(In Formula (1-2), R ¹ and R ² are each independently an organic group, which may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And may contain a bond of heteroatoms, provided that ^one of R ¹ and R ² has a hydroxyl group, and R ¹⁰ and R ^{10 ′} each independently represents a hydrogen atom, A halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, and R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ are each independently a hydrogen atom, a halogen atom, or a hydroxyl group; , Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, anne A niobium group or an organic group, may be different even in the same ^{.R 11, R 12, R 13} , R 14 and ^{R 15,} to form a cyclic structure two or more of them are combined Or may contain a heteroatom bond.)   The photobase generator for a precursor type photosensitive polyimide according to claim 1, wherein a base having a hydroxyl group having a boiling point of 150 ° C or higher and a melting point of 200 ° C or lower is generated.   The photobase generator for precursor type photosensitive polyimide according to claim 1, wherein the base to be generated is an aliphatic amine.   The photobase generator for a precursor type photosensitive polyimide according to any one of claims 1 to 3, wherein the base to be generated does not contain an acidic group.   A negative photosensitive polyimide resin composition comprising a polyimide precursor and the photobase generator according to any one of claims 1 to 4.   The base from which the photobase generator is generated is a base that dissolves 10 parts by weight or more of the polyimide precursor with respect to 100 parts by weight of the base at any temperature of 150 to 200 ° C. Negative photosensitive polyimide resin composition.   The coating material, printing ink, sealing agent, or adhesive, or a forming device for a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped object, an optical member, or a building material. Negative photosensitive polyimide resin composition.   A coating film or a molded body is formed using the negative photosensitive polyimide resin composition according to any one of claims 5 to 7, and the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern. A method for producing a relief pattern, comprising heating after irradiation or simultaneously with irradiation, changing the solubility of the irradiated portion, and then developing. Printed matter, paint, sealant, adhesive, display device, semiconductor, at least partly formed of the negative photosensitive polyimide resin composition according to any one of claims 5 to 7 or a cured product thereof. An article of any of an apparatus, an electronic component, a microelectromechanical system, an optically shaped object, an optical member, or a building material.