JP5011649B2 - Photosensitive resin composition and article - Google Patents

Description

The present invention relates to a photosensitive resin composition having excellent resolution, low cost, and a wide range of options applicable to the structure of a polymer precursor, and in particular, a product or member formed through a patterning step using electromagnetic waves. Polymer precursor resin composition that can be suitably used as an optical material (e.g., optical product, molding material for optical parts, layer forming material, or adhesive), and an article prepared using the resin composition It is about.
Furthermore, the present invention relates to a photosensitive resin composition having excellent resolution, low cost, and a wide range of options applicable to the structure of the polyimide precursor, and in particular, a material of a product or member formed through a patterning process using electromagnetic waves. It relates to a polyimide precursor resin composition that can be suitably used as an optical product, a molding material for an optical component, a layer forming material, an adhesive, or the like, and an article produced using the resin composition. is there.

Polymer materials are used in various products around us because of their easy processing and light weight. The polyimide developed by DuPont in 1955 in the United States has been under development because it has excellent heat resistance and its application to the aerospace field has been studied. Since then, detailed research has been conducted by many researchers, and it has become clear that performance such as heat resistance, dimensional stability, and insulation properties are among the highest in organic materials. Application to materials was promoted. At present, it has been used extensively as a chip coating film in a semiconductor element or as a base material for a flexible printed wiring board.
In recent years, polybenzoxazole, which has similar processing steps, has low water absorption and low dielectric constant, and polybenzimidazole, which has excellent adhesion to the substrate, has been used to solve the problems of polyimide. Has been studied.

  Polyimide is a polymer synthesized from diamine and acid dianhydride. By reacting diamine and acid dianhydride in a solution, it becomes polyamic acid (polyamic acid) which is a precursor of polyimide, and then becomes a polyimide through a dehydration ring closure reaction. In general, since polyimide has poor solubility in a solvent and is difficult to process, it is often made into a polyimide by making it into a desired shape in a precursor state and then heating. Polyimide precursors are often unstable with respect to heat and water and have poor storage stability. In consideration of this point, a polyimide that has been improved so that it can be molded or applied by dissolving in a solvent after introducing a skeleton with excellent solubility in the molecular structure and making it into a polyimide is used. There is a tendency that the chemical resistance and the adhesion to the substrate are inferior to those of the precursor system. Therefore, a method using a precursor and a method using solvent-soluble polyimide are properly used depending on the purpose.

In addition, there has been a demand for patterning polyimide into a desired shape as technology advances. For this reason, polyimide has also been developed that uses electromagnetic waves such as ultraviolet rays to form patterns through processes such as exposure and development. Several methods have been proposed for patterning polyimide. One is patterning in the state of polyimide precursor and then imidizing by heat treatment etc. to obtain polyimide pattern, and the other is forming resist pattern with polyimide or organic substance on polyimide itself, and opening In this method, the pattern is obtained by decomposing or eluting the part with a solution of hydrazine, inorganic alkali, organic alkali or the like, an organic polar solvent, or a mixture thereof.
The former is superior in processing characteristics by using a precursor excellent in solvent solubility, and the latter has an advantage that it is not necessary to perform an imidization process that requires high-temperature heat treatment after pattern formation. It is properly used according to the purpose.

In the semiconductor field, which has achieved remarkable development since the latter half of the 20th century, patternable polyimides of the type mainly utilizing precursors are currently used. One reason for this is that since the polyimide is formed on the silicon wafer, the substrate can withstand a high-temperature heat treatment of 300 ° C. to 400 ° C. necessary for imidization.
Various methods have also been proposed as means for patterning polyimide of the type using a precursor. The typical method is roughly classified into the following two.
(1) A method in which a polyimide precursor itself does not have a patterning capability, a photosensitive resin layer is formed on the surface, and the polyimide precursor is patterned by the pattern of the photosensitive resin.
(2) A method in which a photosensitive site is bonded or coordinated to the polyimide precursor itself and introduced, and a pattern is formed by the action, or a photosensitive component is mixed with the polyimide precursor to form a resin composition, and the photosensitive component A method of pattern formation by the action of. Furthermore, it is a technique that combines the introduction of photosensitive sites and the mixing of photosensitive components.

  As a representative method belonging to the group (1) above, utilizing the fact that the polyamic acid that is a polyimide precursor is soluble in an alkaline solution, a resist capable of alkali development is applied on the coating film, After irradiating the desired shape with electromagnetic waves, simultaneously with developing the resist, the polyamic acid exposed from the opening of the resist appearing in the development is also eluted into the developer to form a pattern, and then an organic solvent such as acetone that does not require polyamic acid The surface resist layer is peeled off, followed by imidization to obtain a polyimide pattern.

On the other hand, as representative methods belonging to the group (2) above:
(A) Polyamic acid, which is a precursor of polyimide, is mixed with a naphthoquinonediazide derivative that acts as a dissolution inhibitor before exposure to electromagnetic waves and generates carboxylic acid and becomes a dissolution accelerator after exposure. A method of forming a pattern by increasing the contrast of the dissolution rate with respect to the developer in the exposed portion, and then imidizing to obtain a polyimide pattern;
(B) Polyamic acid, which is a precursor of polyimide, is mixed with a compound such as a diphenimine derivative that becomes a basic substance that exhibits catalytic action of imidization by exposure to electromagnetic waves, and is exposed by heating at an appropriate temperature after exposure. Since the exposed area is partially imidized by the action of the basic substance generated in the area, the solubility in the developer is lowered, and the contrast between the exposed area and the unexposed area in the developer is increased. A method of forming a pattern and then imidizing completely to obtain a polyimide pattern;

(C) A polyimide precursor having a radically polymerizable skeleton having an ethylenically unsaturated bond bonded thereto is mixed with a photoradical generator to form a cross-linked structure in the exposed area, thereby developing the solution. A technique for reducing the solubility and forming a pattern by increasing the contrast of the dissolution rate of the exposed area and the unexposed area to the developer, followed by imidization to obtain a polyimide pattern;
(D) By mixing a polyamic acid of a polyimide precursor and a skeleton having a radically polymerizable ethylenically unsaturated bond having a basic site, both are ionically bonded, and a photo radical generator is mixed therewith. A cross-linked structure is formed in the exposed area to lower the solubility in the developer, and pattern formation is performed by increasing the contrast between the exposed area and the unexposed area in the developer, followed by imidization and polyimide. Technique to obtain a pattern;
as well as,
(E) A polyamic acid, which is a polyimide precursor, is mixed with a photoacid (or photobase) generator and a crosslinking agent. After exposure, heating is performed, and crosslinking proceeds by the action of the acid (or base) generated by exposure. By reducing the solubility in the developing solution, the contrast of the exposed portion and the unexposed portion with respect to the developing solution is increased to form a pattern, and then imidized to obtain a polyimide pattern, etc. A method has been proposed.

Although the method belonging to the group (1) has a complicated process, the degree of freedom of the composition of the polyimide precursor to be used is large, and since the photosensitive component is not mixed, the final polyimide is other than polyimide. It is characterized by high reliability with no impurities.
On the other hand, in the method belonging to the group (2), since the polyimide precursor (or polyimide precursor resin composition) itself has a pattern forming ability, a resist layer as used in the group (1) is not necessary. Although the process is greatly simplified, if the polyimide precursor itself does not transmit the exposure wavelength sufficiently, electromagnetic waves do not reach the photosensitive component and problems such as reduced sensitivity and pattern formation will occur. Therefore, it is necessary to select a skeleton having a high transmittance with respect to the exposure wavelength.

Among them, since the method (e) belonging to the group (2) can obtain a photosensitive polyimide only by mixing a photoacid (or base) generator at a certain ratio with an existing polyimide precursor, Since the process for producing the resin composition is simple and can be applied to polyimide precursors having any structure, there is an advantage of high versatility. On the other hand, due to the mechanism that only the exposed part is imidized by the catalytic action of the acid or base generated by the irradiation of electromagnetic waves, and that part becomes insoluble in the developer, the polyimide precursor that is originally highly soluble in the developer is The dissolution rate of the exposed part is also fast, and there is a limit to increasing the solubility contrast of the exposed part and the unexposed part.
The higher the solubility contrast between the exposed and unexposed areas, the greater the residual film ratio after development, and the better the pattern can be obtained. Conventionally, the developer concentration and photoacid ( (Or base) It was necessary to adjust the amount of the generator and to add a dissolution accelerator.

JP-A-2-237002

  It is known that N-phenylglycine, which is available on the market at a low price, generates a radical by decarboxylation by absorption of electromagnetic waves according to the following reaction formula (3).

Patent Document 1 discloses a photosensitive resin composition in which a polymer having an N-phenylglycine derivative structure, a polymer thereof, and a compound having an ethylenically unsaturated bond are mixed. The structure derived from glycine is used only as a radical generator, and this document only exemplifies a photosensitive resin composition containing what is generally called an acrylic resin such as acrylic acid. .
The present invention has been achieved in view of the above circumstances, and its purpose is to obtain a large solubility contrast regardless of the type of polyimide precursor, and as a result, the shape is good while maintaining a sufficient process margin. It is in providing the photosensitive resin composition which can obtain a simple pattern.

The photosensitive resin composition according to the present invention is an N-aromatic glycine derivative represented by the following formula (1), a polyimide precursor and / or a polybenzoxazole precursor, and is converted into a final product by the action of a base. It is characterized by containing what changes .

(In the formula, a circle surrounding the symbol A represents an aromatic ring, R ^a , R ^b , R ^c , R ^d and R ^e are hydrogen or a monovalent organic group, m is an integer of 0 or more, n Is an integer of 1 or more, and the sum of m and n is the number of substitutable positions on the aromatic ring, and when m or n is 2 or more, the parts represented by the same symbol in the molecule are different atoms or atoms. Two or more R ^a may be bonded to form a cyclic structure, and R ^b and R ^c existing in the same substituent may be bonded to form a cyclic structure. Provided that at least one of R ^a , R ^b , R ^c , R ^d, or R ^e is an organic group having an ethylenically unsaturated bond. )

  The N-aromatic glycine derivative represented by the above formula (1) has only three functions: 1) a photobase generator, 2) a dissolution accelerator, and 3) a dissolution inhibitor. It acts as a multifunctional photosensitive component.

It is preferable that R ^{e of the} N-aromatic glycine derivative represented by the formula (1) is a hydroxyl group. In this case, the N-aromatic glycine derivative functions as a dissolution accelerator for the non-exposed area during alkali development, and the solubility contrast between the exposed area and the non-exposed area can be increased.

At least one of R ^a , R ^b , R ^c , R ^d, or R ^e of the N-aromatic glycine derivative represented by the formula (1) is an organic group having an ethylenically unsaturated bond. In this case, the ethylenically unsaturated bond of the N-aromatic glycine derivative undergoes a radical polymerization reaction by the action of the radical generated by the decarboxylation reaction of the N-aromatic glycine derivative in the exposed portion. Therefore, the N-aromatic glycine derivative functions as a dissolution inhibitor for the exposed portion, and the solubility contrast between the exposed portion and the non-exposed portion can be increased.

  The wavelength of a high-pressure mercury lamp, which is a general exposure light source, is 436 nm, 405 nm, 365 nm, and the wavelength of the KrF laser is 248 nm. Therefore, the N-aromatic glycine derivative represented by the formula (1) is 436 nm. , 405 nm, 365 nm, and 248 nm are preferably absorbed at at least one wavelength.

  As one of the N-aromatic glycine derivatives represented by the above formula (1), an N-phenylglycine derivative represented by the following formula (2) is preferably used. Since the N-phenylglycine derivative represented by the formula (2) is available at a relatively low cost, it is excellent in cost performance.

(In the formula, R ^{1 to} R ⁵ are each independently a hydrogen atom or a monovalent organic group, and they may be bonded to each other. R ⁶ is a hydrogen atom or a monovalent organic group. R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent organic group, and they may be bonded to each other, and R ⁹ is independently a hydrogen atom or a monovalent organic group, provided that R ^{1 to} R ⁹ is an organic group having an ethylenically unsaturated bond.

As described above, the photosensitive resin composition according to the present invention has three functions of 1) a photobase generator, 2) a dissolution accelerator, and 3) a dissolution inhibitor, so that a wide variety of polymers can be obtained. The precursor can be applied, and the structure of the finally obtained polymer can be selected without being limited by the patterning process. In addition, a photosensitive compound having an N-aromatic glycine skeleton can be obtained at a low cost, and the price as a photosensitive resin composition can be suppressed.
Furthermore, the photosensitive resin composition according to the present invention is a photosensitive polyimide resin composition that can be applied to a wider range of applications by applying a polyimide precursor that has been applied to various applications as a polymer precursor. Available as a thing.
According to the present invention, it is possible to obtain a good pattern shape without applying a dissolution inhibitor or a dissolution inhibitor, even for a polyimide precursor that has conventionally been difficult to obtain a solubility contrast between an exposed area and an unexposed area. it can.
Moreover, since the compound which belongs to the N-aromatic glycine derivative represented by the said Formula (1) can be obtained comparatively cheaply, it is excellent also in cost performance.
In particular, the photosensitive resin composition according to the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film, for example, It is suitable for forming color filters, electronic components, semiconductor elements, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, and other optical members or electronic members.

Moreover, since the photosensitive polymer precursor resin composition according to the present invention can select a polymer precursor having a wide range of structures, the polymer obtained thereby has heat resistance, dimensional stability, insulating properties, etc. Since the function can be imparted, it is suitable as a film or coating film for all known members to which these polymers are applied.
In addition, since the photosensitive polyimide precursor resin composition, which is one form of the polymer precursor resin composition, can select a wide range of polyimide precursors, the resulting polyimide is heat resistant and dimensionally stable. It is suitable as a film or a coating film for all known members to which polyimide is applied because it can impart the functions characteristic of polyimide such as property and insulation.

  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 It means that either acrylate or methacrylate may be used.

  The photosensitive resin composition according to the present invention contains an N-aromatic glycine derivative represented by the following formula (1) (hereinafter sometimes simply referred to as “N-aromatic glycine derivative”) and a polymer precursor. It is characterized by doing.

(In the formula, a circle surrounding the symbol A represents an aromatic ring, R ^a , R ^b , R ^c , R ^d and R ^e are hydrogen or a monovalent organic group, m is an integer of 0 or more, n Is an integer of 1 or more, and the sum of m and n is the number of substitutable positions on the aromatic ring, and when m or n is 2 or more, the parts represented by the same symbol in the molecule are different atoms or atoms. Two or more R ^a may be bonded to form a cyclic structure, and R ^b and R ^c existing in the same substituent may be bonded to form a cyclic structure. Is also good.)

  The N-aromatic glycine derivative used in the present invention is a group of compounds having an N-aromatic glycine skeleton. More specifically, the N-aromatic glycine derivative has a glycine derivative on an aromatic ring represented by a circle surrounding the symbol A. It is a compound in which one or two or more groups having a structure in which one hydrogen is removed from the amino group nitrogen (hereinafter sometimes simply referred to as “glycine derivative group”) are substituted. The aromatic ring represented by the circle surrounding the symbol A is a monocyclic benzene ring, a polycyclic condensed aromatic ring such as a naphthalene ring, an anthracene ring, a pyridine ring, a furan ring, a thioxanthone ring, or a heteroaromatic ring. A polycyclic fused ring containing an aromatic ring and a non-aromatic ring may be used.

  The inventors pay attention to the fact that the N-aromatic glycine derivative becomes an amine after decarboxylation. The exposed portion is cured by imidization using the generated amine as a catalyst, so that the exposed portion and the unexposed portion are separated. It was found that a difference in solubility can be imparted between them.

Further, among N- aromatic glycine derivatives, which distal portion is lost by decarboxylation has a carboxyl group, that is, when used as R ^e is a hydroxyl group in the formula (1) is subjected to exposure In this case, the carboxyl group remains in the unexposed area, and the carboxyl group disappears in the exposed area. Therefore, in the case of developing in an alkaline solution after exposure in a predetermined pattern by combining such an N-aromatic glycine derivative having a carboxyl group at the end with an alkali-soluble polyimide precursor, It has also been found that it functions as a dissolution accelerator.

Furthermore, among N-aromatic glycine derivatives, those having an ethylenically unsaturated bond in the molecule, for example, at least one of R ^a , R ^b , R ^c , R ^d or R ^e in formula (1) It has also been found that when an organic group having an ethylenically unsaturated bond is used, the N-aromatic glycine derivative is polymerized by radicals generated during exposure and functions as a dissolution inhibitor in the exposed area.

That is, the N-aromatic glycine derivative represented by the above formula (1) is
One molecule can have three functions required for forming a photosensitive polymer, that is, a function as a function dissolution inhibitor as a function dissolution accelerator as a photobase generator.
For this reason, the N-aromatic glycine derivative represented by the formula (1) exhibits a plurality of functions by itself, so that it has been difficult to obtain a contrast of solubility so far, and has a high solubility in a developing solution. A large solubility contrast can be obtained even for molecular precursors.
Furthermore, it can also function as a photosensitive polymer precursor without adding a dissolution accelerator or a dissolution inhibitor.

A photosensitive polymer precursor resin composition using a photobase generator has been conventionally known, but a compound having three functions of a photobase generator, a dissolution accelerator, and a dissolution inhibitor in one molecule. What was used has never been proposed before.
In the present invention, a single compound exerts these three functions, whereby a photosensitive resin composition can be more easily prepared, and a wide range of applicable polymer precursors can be selected. Suitable compounds in the field where the characteristics of the photosensitive polymer precursor resin composition and the cyclized product can be utilized, particularly the photosensitive polyimide precursor resin composition and its imide which are typical examples thereof The preferred application in the field where the characteristics of the chemicals can be utilized.

  As a typical example of the N-aromatic glycine derivative represented by the above formula (1), an N-phenylglycine derivative represented by the following formula (2) (hereinafter sometimes simply referred to as “N-phenylglycine derivative”) Will be explained. The characteristics, advantages, and other contents explained regarding the N-phenylglycine derivative of the formula (2) are explanations common to all N-aromatic glycine derivatives represented by the formula (1) unless otherwise contradicted.

(In the formula, R ^{1 to} R ⁵ are each independently a hydrogen atom or a monovalent organic group, and they may be bonded to each other. R ⁶ is a hydrogen atom or a monovalent organic group. R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent organic group, and they may be bonded to each other, and R ⁹ is independently a hydrogen atom or a monovalent organic group.)

R ^{1 to} R ⁵ of the N-phenylglycine derivative represented by the formula (2) correspond to ^Ra of the N-aromatic glycine derivative represented by the formula (1), and other than a hydrogen atom at these positions. Substituents may be introduced. If the N-phenylglycine derivative has a skeleton of the formula (2), the same effect can be expected even if a substituent is introduced at the positions of R ^{1 to} R ⁵ .

Examples of the monovalent organic group that can be introduced on the aromatic ring as the substituents R ^{1 to} R ⁵ include a halogen atom, a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a tertiary amino group, and cyano. Group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, saturated or unsaturated alkyl group, saturated or unsaturated halogenated alkyl group, or aromatic such as phenyl or naphthyl Group, allyl group and the like.
R ^{1 to} R ⁵ may be the same as or different from each other. Two or more groups of R ^{1 to} R ⁵ may be bonded to each other to form a cyclic structure.

  Furthermore, a monovalent ethylenically unsaturated bond-containing group having one or more radically polymerizable ethylenically unsaturated bonds in the structure in order to impart a dissolution inhibiting effect. The ethylenically unsaturated bond-containing group is a substituent having one or more ethylenically unsaturated bonds. Specific examples include an allyl group, a (meth) acryloyl group, an allyloxy group, and 2- (meth) acryloyloxy. Ethyloxy group, 2- (meth) acryloyloxypropyloxy group, 2- (meth) acryloyloxyethylamino group, 2- (meth) acryloyloxypropylamino group, 2-hydroxy-3- (meth) acryloyloxypropyloxy Groups, and derivatives thereof, but are not limited thereto.

In the N-phenylglycine derivative represented by the formula (2), the position of the R ⁶ position corresponds to R ^b of the N-aromatic glycine derivative represented by the formula (1), and other than a hydrogen atom at this position. May be introduced. The introduction of a substituent at the position of R ⁶ changes the ease of base generation and the strength of the generated base, and affects the performance as a photobase generator. It is preferable to improve the performance as a photobase generator.
From this viewpoint, the monovalent organic group that can be introduced onto the nitrogen atom of the amino group includes, for example, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or an aromatic group such as phenyl or naphthyl. And groups having a hydrocarbon skeleton such as an allyl group.
In the case of having a hydrogen atom at the position of R ⁶ , it is easy to generate a base by a decarboxylation reaction, so that the irradiation sensitivity during exposure can be increased. On the other hand, when a group having a hydrocarbon skeleton at the position of R ⁶ , particularly a group having about 1 to 20 carbon atoms, preferably about 1 to 8 carbon atoms, a strong base is generated, an imidization reaction is generated. Can be promoted.

Further, in order to impart a dissolution inhibiting effect, monovalent ethylene having one or more radically polymerizable ethylenically unsaturated bonds in the structure, such as those exemplified as R ^{1 to} R ⁵ , at the position of R ^6. An unsaturated bond-containing group or the like may be introduced.
These ethylenically unsaturated bond-containing groups, as disclosed in JP-A-2-237002, when the nitrogen atom contained in the N-phenylglycine derivative is secondary nitrogen (secondary amino group), It can introduce | transduce by the method of making the compound which has both a glycidyl group and ethylenically unsaturated bonds like glycidyl methacrylate react.

In the N-phenylglycine derivative represented by the formula (2), the positions of R ⁷ and R ⁸ correspond to R ^c and R ^d of the N-aromatic glycine derivative represented by the formula (1), respectively. A substituent other than a hydrogen atom may be introduced at the position. Introduction of substituents at the positions of R ⁷ and R ⁸ changes the likelihood of decarboxylation, and as a result, affects the performance as a photobase generator in the sense of ease of base generation, Further, it affects the performance as a dissolution inhibitor in the exposed area in the sense that radicals are easily generated. Therefore, the substituent introduced at this position is preferably one that improves decarboxylation reactivity.

From this viewpoint, examples of the monovalent organic group that can be introduced at the position of R ⁷ and / or R ⁸ include, for example, a halogen atom, a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, and a tertiary amino group. Group, cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, saturated or unsaturated alkyl group, saturated or unsaturated halogenated alkyl group, or phenyl, naphthyl And aromatic groups such as allyl groups. R ⁷ and R ⁸ may be the same as or different from each other. R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure.
Furthermore, in order to impart a dissolution inhibiting effect, one or more radically polymerizable ethylenically unsaturated bonds, such as those exemplified as R ^{1 to} R ⁵ , may be present in the structure at the positions of R ⁷ and / or R ^8. A monovalent ethylenically unsaturated bond-containing group or the like may be introduced.

Position of R ⁹ in N- phenylglycine derivative represented by the formula (2) corresponds to R ^e of N- aromatic glycine derivative represented by the formula (1), the substituents other than a hydrogen atom in this position May be introduced.
Examples of the monovalent organic group that can be introduced at the position of R ⁹ include a halogen atom, a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a tertiary amino group, a cyano group, a silyl group, a silanol group, Alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, saturated or unsaturated alkyl group, saturated or unsaturated halogenated alkyl group, or aromatic group such as phenyl and naphthyl, allyl group, etc. It is done.

As long as the N-phenylglycine derivative has a skeleton of the formula (2), the same effect can be expected even if a substituent is introduced at the position of R ⁹ , but from the viewpoint of ease of decarboxylation, From the viewpoint of the dissolution promoting effect, R ⁹ preferably has a hydroxyl group and the N-phenylglycine derivative has a carboxylic acid at the end.
Further, in order to impart a dissolution inhibiting effect, monovalent ethylene having one or more radically polymerizable ethylenically unsaturated bonds in the structure, such as those exemplified as R ^{1 to} R ⁵ , at the position of R ^9. An unsaturated bond-containing group or the like may be introduced.

Each substituent R ^{1 to} R ⁹ may be introduced in the form of a reaction intermediate, or may be introduced after the form of an N-phenylglycine derivative.
Moreover, it is possible to adjust the wavelength of light to be absorbed by introducing one or more of substituents R ^{1 to} R ⁹ into the molecule of the N-phenylglycine derivative, and introducing the substituent. It is also possible to absorb the desired wavelength.
In particular, since the substituents R ^{1 to} R ⁵ on the aromatic ring have a low possibility of affecting the performance as a photobase generator, the types of substituents are relatively free from the viewpoint of adjusting the absorption wavelength. Can be selected.

  Interpretation of the Ultraviolet Spectra of Natural Products (AIScott 1964) and identification methods by spectrum of organic compounds as a guide to what substituents should be introduced to shift the absorption wavelength with respect to the desired wavelength You can refer to the table described in the fifth edition (RMSilverstein 1993).

The polymer precursor used in the photosensitive resin composition of the present invention refers to a substance that itself is a polymer and finally becomes a polymer that exhibits the desired physical properties by intramolecular reaction. Examples thereof include those formed from a repeating unit having a cyclic structure by an intramolecular ring-closing reaction involving elimination of water molecules and / or alcohol molecules, such as a polyimide precursor and a polybenzoxazole precursor.
In the present invention, the polymer precursor may be any polyimide precursor from the mechanism as long as it is a polyimide precursor or a polybenzoxazole precursor, and two or more kinds of polymer precursors synthesized separately. A mixture of
In the case of using an alkali solution soluble in an alkaline solution as a polyimide precursor or a polybenzoxazole precursor, and using an N-aromatic glycine derivative in combination with a carboxyl group-containing one at its molecular terminal, In the exposed area, the solubility is high due to the action of the carboxyl group, but in the exposed area, the dissolution promoting action due to the carboxyl group is lost due to the decarboxylation reaction, and the solubility contrast between the exposed area and the non-exposed area can be improved. . Here, a polyamic acid is suitably used as the alkali-soluble polyimide precursor, and a polyamide alcohol is suitably used as the polybenzoxazole precursor.

  In addition, from the viewpoint of excellent heat resistance and dimensional stability of the finally obtained polyimide, the portion derived from acid dianhydride has an aromatic structure, and the portion derived from diamine also has an aromatic structure. It is preferable that it is a wholly aromatic polyimide precursor. Therefore, the structure derived from the diamine component is also preferably a structure derived from an aromatic diamine. Here, the wholly aromatic polyimide precursor is a polyimide precursor obtained by copolymerization of an aromatic acid component and an aromatic amine component, or polymerization of an aromatic acid / amino component, and a derivative thereof. The aromatic acid component is a compound in which all four acid groups forming the polyimide skeleton are substituted on the aromatic ring, and the aromatic amine component is the two amino groups forming the polyimide skeleton. Both are compounds substituted on the aromatic ring, and the aromatic acid / amino component is a compound in which both the acid group and amino group forming the polyimide skeleton are substituted on the aromatic ring. However, as is clear from the specific examples of raw materials described later, it is not necessary for all acid groups or amino groups to be present on the same aromatic ring.

  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 polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic dianhydride. , Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 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-dicarbo) Ciphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoro Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-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} propa 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, Screw {4- [3- (1,2 -Dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-di Carboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafulpropane Dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-propane dianhydride, 2,3,6 , 7-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4 Benzenetetracarboxylic dianhydride, 3 4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride . 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, but p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -Diaminodiph Nylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 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-hexa Fluoropropane, 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-aminophenyl) -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-bis (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-dito Trifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) 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-amino) Phenoxy) 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 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, , 3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis ( -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-diaminododecane, 1,2-diaminocyclohex 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] A diamine obtained by substituting some or all of the hydrogen atoms on the aromatic ring of the above diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group. Can be used.
Furthermore, depending on the purpose, any one or two or more of the ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate 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 (4). Specific examples include benzidine and the like.

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

Furthermore, in the above formula (4), it is also possible to use a diamine having a substituent at a position where the amino group on the benzene ring is not substituted without being involved in the bond with another benzene ring. These substituents are monovalent 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 more 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.

Next, although the method of synthesizing the N-phenylglycine derivative of the present invention and the polyimide precursor will be specifically illustrated, the present invention is not limited to this.
The N-phenylglycine derivative can be synthesized by reacting N-phenylglycine with glycidyl methacrylate. N-phenylglycine sodium salt and polymerization inhibitor hydroquinone are dissolved in a distilled water-methanol mixed solvent, stirred while keeping the liquid temperature at 40 ° C. to 50 ° C., and glycidyl methacrylate is slowly added dropwise. After stirring for 2 to 7 hours, distilled water is added, the mixture is acidified with 1N hydrochloric acid, and the resulting precipitate is filtered and dried to obtain the desired product.
The N-phenylglycine derivative can also be obtained by reacting 4-vinylaniline and ethyl bromoacetate. 4-vinylaniline, potassium carbonate and dimethylformamide are stirred at room temperature. Thereto, 4-vinylaniline and equimolar ethyl bromoacetate are gradually added, and the mixture is stirred at room temperature for 5 to 48 hours. The reaction solution is poured into ice water, and the deposited precipitate is filtered and dried. The precipitate can be hydrolyzed with alkali hydroxide or the like to obtain the desired product.

  The N-phenylglycine derivative of the present invention synthesized as described above is used to sufficiently exhibit functions such as generation of a photobase for imidization, promotion of dissolution in an unexposed area, and inhibition of dissolution in an exposed area. It is necessary to have absorption for at least part of the exposure wavelength. The wavelength of a high-pressure mercury lamp that is a general exposure light source includes 436 nm, 405 nm, and 365 nm. The wavelength of the KrF laser is 248 nm. From this point of view, the N-phenylglycine derivative is an electromagnetic wave having at least one wavelength among electromagnetic waves having wavelengths of at least 436 nm, 405 nm, 365 nm, and 248 nm when exposure is performed using a high-pressure mercury lamp that is a general exposure light source. It is preferable that it has absorption with respect to.

On the other hand, in order to synthesize a polyimide precursor, for example, while cooling a solution obtained by dissolving 4,4′-diaminodiphenyl ether as an amine component in an organic polar solvent such as N-methylpyrrolidone, there is equimolar 3,4 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 order to increase the sensitivity when the polyimide precursor is a photosensitive resin composition and obtain a pattern shape that accurately reproduces the mask pattern, at least 5% or more with respect to the exposure wavelength when the film thickness is 1 micron. It is preferable to show the transmittance | permeability of 15% or more.
That the transmittance | permeability of a polyimide precursor is high with respect to an exposure wavelength means that there is little loss of light, and a highly sensitive photosensitive resin composition can be obtained.
When exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a film having a thickness of 1 μm has a transmittance with respect to an electromagnetic wave having one wavelength of at least 436 nm, 405 nm, and 365 nm. When the film is formed, it is preferably 5% or more, more preferably 15%, and further preferably 50% or more.
In the case of exposure with a KrF laser having a wavelength of 248 nm, the transmittance at 248 nm is preferably 5% or more, more preferably 15%, more preferably 50% or more when formed on a film having a thickness of 1 μm. .

The weight average molecular weight of the polyimide precursor is preferably in the range of 3,000 to 1,000,000, more preferably in the range of 5,000 to 500,000, although it depends on the application. More preferably, it is in the range of 1,000,000 to 500,000. When the weight average molecular weight is 3,000 or less, 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 is performed to obtain polyimide. On the other hand, when it exceeds 1,000,000, the viscosity increases and the solubility also decreases, so that 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), which may be the molecular weight of the polyimide precursor itself, or after chemical imidization treatment with acetic anhydride or the like. May be good.

The photosensitive resin composition according to the present invention may be a simple mixture of only a photosensitive compound having an N-aromatic glycine skeleton, a polyimide precursor, and a solvent. A photosensitive resin composition may be prepared by blending a non-polymerizable binder resin other than the polyimide precursor according to the invention and other components.
Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive 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.

  Usable general-purpose solvents include, for example, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other ethers; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; acetic acid Ethyl, butyl acetate, vinegar n-propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, dimethyl oxalate , Esters such as methyl lactate and ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1- Halogenated hydrocarbons such as chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N-dimethylphenol Amides such as muamide and N, N-dimethylacetamide; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, and other organic polar solvents, and the like. , Aromatic hydrocarbons such as benzene, toluene and xylene, and other organic nonpolar solvents. These solvents are used alone or in combination.

  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 resin composition is formed, the contrast of the dissolution rate of the exposed area and the unexposed area 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 Such as 1-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-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethi Thioxanthones such as thioxanthone, 2-chlorothioxanthone and 2,4-diisopropylpyroxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; monoacylphosphine oxide or bisacyl such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide Phosphine oxides; benzophenones such as benzophenone; and xanthones.

To the photosensitive resin composition of the present invention, other photosensitive components that generate an acid or a base by light may be added as an auxiliary role of the photosensitive compound having an N-aromatic glycine skeleton.
Compounds that generate an acid by light include photosensitive diazoquinone compounds having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. US Pat. Nos. 2,772,972, 2,797, No. 213, No. 3,669,658.
Further, 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 it can. When exposed to actinic rays, the molecular structure changes to a structure having a pyridine skeleton through an intramolecular transition and becomes basic, and the subsequent heat treatment at 130 ° C. or higher results in the polyimide precursor. Imidization proceeds, solubility decreases, and a good negative pattern can be formed.

  In order to impart processing characteristics and various functionalities to the resin composition according to the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles, sensitizers, 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.

In the photosensitive resin composition according to the present invention, the N-aromatic glycine derivative represented by the formula (1) is usually 0.1% with respect to the solid content of the polymer precursor contained in the photosensitive resin composition. It is contained in the range of -95% by weight, preferably 0.5-60% by weight. If it is less than 0.1%, it is difficult to obtain the effect of addition, and if it exceeds 95%, it becomes difficult to satisfy the required physical properties.
Moreover, the mixture ratio of other arbitrary components has the preferable range of 0.1 to 95 weight% with respect to the whole solid content of the photosensitive resin composition. If it is less than 0.1% by weight, the effect of adding the additive is difficult to be exhibited, and if it exceeds 95% by weight, the characteristics are hardly reflected in the final product. In addition, solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

The photosensitive resin composition according to the present invention can be used in various coating processes and molding processes to produce films and molded articles having a three-dimensional shape.
When the photosensitive resin composition according to the present invention is applied on a support and exposed to a predetermined pattern using light such as electromagnetic waves, the N-aromatic glycine derivative undergoes a decarboxylation reaction at the exposed portion. A tertiary amine or a tertiary amine is formed. Accordingly, the N-aromatic glycine derivative functions as a photobase generator and imidizes the polyimide precursor in the exposed portion.
Further, when R ^e in the formula (1) is a hydroxyl group, due to the presence of carboxyl groups at the ends of the N- aromatic glycine derivatives, the solubility in an alkali developing solution by the presence of carboxyl groups in the non-exposed portion However, in the exposed area, the carboxyl group is decomposed by the decarboxylation reaction, and the action of promoting the solubility in the alkaline developer is weakened or completely lost.
As a result, using N- aromatic glycine derivatives is R ^e is a hydroxyl group in the formula (1), in the case of alkali development, N- aromatic glycine derivative acts as a dissolution promoter for the non-exposed portion, the exposure The solubility contrast between the part and the non-exposed part can be increased.
Further, when at least one of R ^a , R ^b , R ^c , R ^d or R ^{e in} the formula (1) is a group having an ethylenically unsaturated bond, N-aromatic glycine is used in the exposed area. By the action of radicals generated by the decarboxylation reaction of the derivative, the ethylenically unsaturated bond of the N-aromatic glycine derivative undergoes a radical polymerization reaction.
As a result, when the substituent of the N-aromatic glycine derivative is a group having an ethylenically unsaturated bond, the N-aromatic glycine derivative functions as a dissolution inhibitor for the exposed area, and the exposed area and the non-exposed area. The solubility contrast of can be increased.
Therefore, the photosensitive resin composition according to the present invention can be used as a negative photosensitive resin composition in which an exposed portion is cured.

  As described above, according to the photosensitive resin composition of the present invention, the N-aromatic glycine derivative not only promotes imidization but also acts as a multifunctional photosensitive component. A good pattern shape can be obtained without applying a dissolution inhibitor or a dissolution inhibitor even for a polyimide precursor in which it is difficult to obtain a solubility contrast between exposed portions.

The coating film of the photosensitive resin composition according to the present invention may be developed immediately after exposure, but is preferably subjected to heat treatment between the exposure step and the development step. The temperature of the heat treatment at this stage is usually about 60 ° C to 180 ° C.
Further, heat treatment may be performed after development. The temperature of the heat treatment at this stage is usually about 150 ° C. to 400 ° C.
This heat treatment may be any method as long as it is a known method, and specific examples thereof include, but are not particularly limited to, heating with a circulating oven or hot plate in an air or nitrogen atmosphere.

The polyimides and polybenzoxazoles obtained from the photosensitive resin composition of the present invention are good because the original properties such as heat resistance, dimensional stability and insulation are not impaired.
For example, the 5% weight loss temperature measured in nitrogen of polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably 250 ° C. or higher, more preferably 300 ° C. or higher. In particular, when used in applications such as electronic parts that pass through the solder reflow process, if the 5% weight loss temperature is 300 ° C. or less, defects such as bubbles occur due to the decomposition gas generated in the solder reflow process. There is a fear. Here, the 5% weight reduction temperature is the time when the weight of the sample is reduced by 5% from the initial weight when the weight loss is measured using a thermogravimetric analyzer (in other words, the sample weight becomes 95% of the initial weight). Temperature). Similarly, the 10% weight reduction temperature is a temperature at which the sample weight is reduced by 10% from the initial weight.

The glass transition temperature of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance, but in applications where a thermoforming process is considered like an optical waveguide, It is preferable to show a glass transition temperature of about 120 ° C. to 380 ° C., and more preferable to show a glass transition temperature of about 200 ° C. to 380 ° C.
From the viewpoint of the dimensional stability of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention, the linear thermal expansion coefficient is preferably 60 ppm or less, and more preferably 40 ppm or less. In the case of forming a film on a silicon wafer in a manufacturing process of a semiconductor element or the like, 20 ppm or less is more preferable from the viewpoint of adhesion and warpage of the substrate.

  As described above, in the photosensitive resin composition according to the present invention, the photosensitive compound having an N-aromatic glycine skeleton is referred to as 1) a photobase generator, 2) a dissolution accelerator, and 3) a dissolution inhibitor. By having three functions, a wide variety of polymer precursors can be applied, and the structure of the finally obtained polymer can be selected without being limited by the pattern formation process. In addition, a photosensitive compound having an N-aromatic glycine skeleton can be obtained at a low cost, and the price as a photosensitive resin composition can be suppressed.

  The photosensitive resin composition according to the present invention includes printing inks, adhesives, fillers, semiconductor elements, electronic materials, optical circuit components, molding materials, resist materials, building materials, three-dimensional modeling, optical members, and the like. It can be used for all known fields and products used.

  The photosensitive resin composition according to the present invention is used in a wide range of fields and products in which properties such as heat resistance, dimensional stability, and insulation are effective, such as paints or printing inks, color filters, and films for flexible displays. , Electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, holograms, optical members, or a photosensitive resin composition according to the present invention Printed matter, color filter, flexible display film, semiconductor device, electronic component, interlayer insulating film, wiring coating film, optical circuit, optical circuit component, antireflection film, at least part of which is formed by the intramolecular ring closure Articles of either holograms, optical members or building materials are provided.

  In particular, the photosensitive resin composition according to the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film, for example, It is suitable for forming color filters, electronic components, semiconductor elements, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, and other optical members or electronic members.

(Production Example 1)
N-Phenylglycine (1.57 g, 10 mmol) and 400 mg of sodium hydroxide dissolved in 5 ml of distilled water are placed in a 50 mL (ml) flask and stirred at room temperature. Thereto, 10 mg of hydroquinone and 5 ml of methanol are added and completely dissolved, and then 1.42 g (10 mmol) of glycidyl methacrylate is gradually added dropwise. After stirring for 2 hours after completion of the dropwise addition, 1N hydrochloric acid was added to neutralize and a white precipitate was deposited. The precipitate was dried under reduced pressure to obtain 2.9 g of photosensitive compound 1. The structure of the photosensitive compound 1 is shown below.

（製造例２）
４−ビニルアニリン １．１９ｇ（１ｍｍｏｌ）と、炭酸カリウム １．５２ｇ（１．１ｍｍｏｌ）と、脱水されたジメチルホルムアミド ２０ｍｌを１００ｍｌのなすフラスコへ入れ、撹拌する。反応容器を氷浴で冷却しながらブロモ酢酸エチル １．８４ｇ（１．１ｍｍｏｌ）を徐々に滴下し、滴下終了後、室温へ戻す。２４時間後、氷水１Ｌの中へ投入し、析出した沈殿を減圧乾燥し、Ｎ−フェニルグリシンエチルエステルの４−ビニル化物を１．６５ｇ得た。その化合物 １ｇを、３ｍｌのメタノールに溶かし、薄層クロマトグラフィーで、反応の経過を追跡しながら、水酸化リチウム飽和メタノール溶液を滴下し、原料のスポットが消失した時点で滴下を終了し、その反応液を１規定塩酸で中和した後、蒸留水へ投入し、析出した沈殿を集め減圧乾燥し、４２０ｍｇの感光性化合物２を得た。感光性化合物２の構造を以下に示す。

(Production Example 2)
4.19 g (1 mmol) of 4-vinylaniline, 1.52 g (1.1 mmol) of potassium carbonate, and 20 ml of dehydrated dimethylformamide are put into a 100 ml flask and stirred. While the reaction vessel is cooled in an ice bath, 1.84 g (1.1 mmol) of ethyl bromoacetate is gradually added dropwise. After 24 hours, it was poured into 1 L of ice water, and the deposited precipitate was dried under reduced pressure to obtain 1.65 g of 4-vinylated product of N-phenylglycine ethyl ester. 1 g of the compound was dissolved in 3 ml of methanol, a lithium hydroxide saturated methanol solution was added dropwise while monitoring the progress of the reaction by thin layer chromatography, and the addition was terminated when the spot of the raw material disappeared, and the reaction The solution was neutralized with 1N hydrochloric acid and then poured into distilled water, and the deposited precipitate was collected and dried under reduced pressure to obtain 420 mg of photosensitive compound 2. The structure of the photosensitive compound 2 is shown below.

（製造例３）
４，４’−ジアミノジフェニルエーテル １．２０ｇ（６ｍｍｏｌ）を５０ｍｌの3つ口フラスコに投入し、５ｍｌの脱水されたN-メチル-2-ピロリドン（NMP）に溶解させ窒素気流下、氷浴で冷却しながら撹拌した。そこへ、少しずつピロメリット酸二無水物 １．３１ｇ（６ｍｍｏｌ）を添加し、添加終了後、氷浴中で５時間撹拌し、その溶液を、脱水されたジエチルエーテルによって再沈殿し、その沈殿物を室温で減圧下、１７時間乾燥し、白色固体を２．１１ｇ（ポリイミド前駆体１）を得た。

(Production Example 3)
4.20 g (6 mmol) of 4,4′-diaminodiphenyl ether was put into a 50 ml three-necked flask, dissolved in 5 ml of dehydrated N-methyl-2-pyrrolidone (NMP), and cooled in an ice bath under a nitrogen stream. While stirring. Pyromellitic dianhydride 1.31 g (6 mmol) was added little by little, and after the addition was completed, the mixture was stirred in an ice bath for 5 hours, and the solution was reprecipitated with dehydrated diethyl ether. The product was dried at room temperature under reduced pressure for 17 hours to obtain 2.11 g (polyimide precursor 1) of a white solid.

Example 1
400 mg of polyimide precursor 1, photosensitive compounds 1 and 2 as photosensitive compounds, and 200 mg each of N-phenylglycine were dissolved in 3 ml of NMP to obtain three types of photosensitive resin compositions (photosensitive resin composition 1-3).
Each photosensitive resin composition was spin-coated on glass to a final film thickness of 2 μm and dried on a hot plate at 80 ° C. for 30 minutes. Then, 2J ultraviolet irradiation was performed in terms of h-line conversion with a manual exposure device (Dainippon Screen Co., Ltd., MA-1200), and then heated on a hot plate at 160 ° C. for 30 minutes, and then tetramethylammonium hydroxide. 2. Dipped in 38% solution. As a result, the pattern of the photosensitive resin composition 3 could be obtained with all of the photosensitive resin compositions 1 to 3, although the film thickness of the pattern was large.
Furthermore, those samples were heated at 300 ° C. for 1 hour to perform imidization. From these results, it was revealed that the photosensitive resin composition of the present invention can form a good pattern.

Claims (20)

It contains an N-aromatic glycine derivative represented by the following formula (1) and a polyimide precursor and / or a polybenzoxazole precursor that changes to a final product by the action of a base. A photosensitive resin composition.

(In the formula, a circle surrounding the symbol A represents an aromatic ring, R ^a , R ^b , R ^c , R ^d and R ^e are hydrogen or a monovalent organic group, m is an integer of 0 or more, n Is an integer of 1 or more, and the sum of m and n is the number of substitutable positions on the aromatic ring, and when m or n is 2 or more, the parts represented by the same symbol in the molecule are different atoms or atoms. Two or more R ^a may be bonded to form a cyclic structure, and R ^b and R ^c existing in the same substituent may be bonded to form a cyclic structure. (However, at least one of R ^a , R ^b , R ^c , R ^d, or R ^e is an organic group having an ethylenically unsaturated bond.) The photosensitive resin composition according to claim 1, wherein R ^e of the N-aromatic glycine derivative represented by the formula (1) is a hydroxyl group.   The photosensitive resin composition according to claim 1 or 2, wherein the N-aromatic glycine derivative represented by the formula (1) has absorption at at least one wavelength among electromagnetic waves having wavelengths of 436 nm, 405 nm, 365 nm, and 248 nm. object. The photosensitive resin composition according to claim 1 or 3, wherein the N-aromatic glycine derivative represented by the formula (1) is an N-phenylglycine derivative represented by the following formula (2).

(In the formula, R ^{1 to} R ⁵ are each independently a hydrogen atom or a monovalent organic group, and they may be bonded to each other. R ⁶ is a hydrogen atom or a monovalent organic group. R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent organic group, and they may be bonded to each other, and R ⁹ is independently a hydrogen atom or a monovalent organic group, provided that R ^{1 to} R ⁹ is an organic group having an ethylenically unsaturated bond.)   The photosensitive resin composition according to claim 1, wherein the polyimide precursor and the polybenzoxazole precursor are soluble in an alkaline solution.   The photosensitive resin composition according to claim 1, wherein the polyimide precursor is a polyamic acid.   Used as paint or printing ink, or color filter, flexible display film, electronic component, interlayer insulation film, wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material The photosensitive resin composition according to claim 6.   Printed matter in which at least a part is formed by the photosensitive resin composition according to any one of claims 1 to 7 or an imidized product thereof.   The color filter in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   The film for flexible displays in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   A semiconductor device, at least a part of which is formed of the photosensitive resin composition according to claim 1 or an imidized product thereof.   The electronic component in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   The interlayer insulation film in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   The wiring coating film in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   The optical circuit in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   The optical circuit component in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   An antireflection film, at least part of which is formed of the photosensitive resin composition according to any one of claims 1 to 7 or an imidized product thereof.   A hologram, at least part of which is formed of the photosensitive resin composition according to claim 1 or an imidized product thereof.   The optical member in which at least one part is formed with the photosensitive resin composition in any one of the said Claims 1-7, or its imidation thing.   A building material, at least part of which is formed of the photosensitive resin composition according to claim 1 or an imidized product thereof.