JP5152350B2 - Photosensitive resin composition - 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. A polymer precursor resin composition that can be suitably used as a material (for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material, or an adhesive), and the resin composition It relates to the manufactured article.
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 a polyimide precursor or polybenzoxazole precursor, and is particularly formed through a patterning process using electromagnetic waves. A precursor resin composition of polyimide or polybenzoxazole which can be suitably used as a material of a product or member (for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material or an adhesive), and The present invention relates to an article produced using the resin composition.

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, in order to solve the problems of polyimide, similar processing steps have been applied, and polybenzoxazole, which exhibits low water absorption and low dielectric constant, and polybenzimidazole, which has excellent adhesion to the substrate, are also energetic. 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 of them is a method of obtaining a polyimide pattern by performing patterning by exposure and development in the state of a polyimide precursor, and then imidizing by heat treatment or the like. The other is that a resist pattern is formed of organic matter, metal, etc. on polyimide itself which is not photosensitive itself, and the opening is formed by a solution of hydrazine, inorganic alkali, organic alkali, etc. or an organic polar solvent, or those The pattern is obtained by treating with a mixture of
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 a type of polyimide that uses 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 electromagnetic wave in the desired shape, 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 insoluble in the 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) The polyamic acid of the polyimide precursor is mixed with a naphthoquinonediazide derivative that acts as a dissolution inhibitor before exposure to electromagnetic waves and generates a carboxylic acid and serves as a dissolution accelerator after exposure. A method of obtaining a polyimide pattern by forming a pattern by increasing the contrast of the dissolution rate with respect to the developer of the part, and then imidizing;
(B) The polyamic acid of the polyimide precursor is mixed with a compound such as a dihydropyridine derivative that becomes a basic substance exhibiting imidization catalysis by exposure to electromagnetic waves, and after exposure, the exposed portion is heated at an appropriate temperature. Since the exposed part is partially imidized by the action of the basic substance generated in the pattern, the solubility in the developer is lowered, and the pattern is obtained by increasing the contrast of the dissolution rate in the developer between the exposed part and the unexposed part. A method of forming and then completely imidizing 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) The polyamic acid of the polyimide precursor is mixed with a photoacid (or photobase) generator and a crosslinking agent, and after exposure, heating is performed to advance crosslinking by the action of the acid (or base) generated by exposure. , By reducing the solubility in the developer, to increase the contrast of the dissolution rate of the exposed and unexposed areas with the developer, to form a pattern, then imidize 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 sufficiently transmit the exposure wavelength, electromagnetic waves do not reach the photosensitive component, causing problems such as reduced sensitivity and pattern formation. 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 exposed. The dissolution rate of the part was also high, and there was a limit in increasing the solubility contrast between 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.

  The present invention has been accomplished in view of the above circumstances, and its purpose is to obtain a large solubility contrast regardless of the type of polymer precursor, and as a result, the shape is maintained while maintaining a sufficient process margin. It is providing the photosensitive resin composition which can obtain a favorable pattern.

The photosensitive resin composition according to the present invention, a salt of an aromatic component containing carboxylic acid and a tertiary amine represented by the following formula to a light decarboxylation (1), containing a polymer precursor, the high The molecular precursor is a polymer precursor that itself is a polymer and becomes a polymer that finally shows a desired physical property by an intramolecular reaction by the action of a base .

(In the formula, R ^{1 to} R ⁵ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. R ⁶ and R ⁷ are each independently hydrogen or a monovalent organic group, and they may be the same or different, and the two may be the same as each other. R ^{8 to} R ¹⁰ are each independently a monovalent organic group, and two or more of them may be the same or different from each other, and may be bonded to form a cyclic structure. Two or more of them may be combined to form a cyclic structure.)
Salts of carboxylic acids with amines to light decarboxylation upon irradiation with electromagnetic waves can no longer maintain the state of a salt by light decarboxylation, so to generate an amine base, itself a polymer, molecule by the action of a base finally against the polymer precursor as a polymer showing properties of interest by the inner reaction, it acts as a very effective photosensitive components.
In addition, even if the polymer precursor itself does not eventually change to a final product due to the action of the base, a reaction system in which the target reaction proceeds due to the action of the base when viewed as the entire photosensitive resin composition. If it is a composition containing carboxylic acid and amine salt which photodecarboxylates, it is effective as a photosensitive component.

  The salt of the aromatic component-containing carboxylic acid represented by the above formula (1) and the tertiary amine undergoes a decarboxylation reaction due to absorption of electromagnetic waves and generates a base. Therefore, the salt of this aromatic component-containing carboxylic acid and amine is a polymer precursor that catalyzes a reaction in which a base changes to a final product, such as a polyimide precursor, or a target reaction caused by the action of a base. It acts as a very effective photosensitive component for compositions containing systems in which

At least one of R ^{1 to} R ⁵ of the aromatic component-containing carboxylic acid constituting the salt of the aromatic component-containing carboxylic acid represented by the formula (1) and the tertiary amine is represented by the following formula (2). It is preferable that it is a structure.

(In the formula, R ^{11 to} R ¹⁵ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. It may be bonded to form a ring structure.)

  In this case, the absorption wavelength of the salt of the aromatic component-containing carboxylic acid and the tertiary amine is shifted to the longer wavelength side, and can be applied to a polymer precursor having a wider range of structures, and the sensitivity is further improved. .

  As one of the aromatic component-containing carboxylic acids constituting the salt of the aromatic component-containing carboxylic acid represented by the formula (1) and the tertiary amine, a ketoprofen derivative represented by the following formula (3) is preferably used. It is done. The ketoprofen derivative represented by the formula (3) is excellent in cost performance because it can be obtained at a relatively low cost.

(In the formula, R ^{16 to} R ²⁴ are each independently a hydrogen atom or a monovalent organic group, and two or more of them may be the same or all may be different. R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a straight chain, branched or cyclic hydrocarbon group, and they may be the same or different. In addition, they may be bonded to each other to form a cyclic structure.)

  The amine used for the salt of the carboxylic acid and tertiary amine to be photodecarboxylated is preferably an aliphatic tertiary amine from the viewpoint of using a highly basic amine.

  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 salt of the aromatic component-containing carboxylic acid and the tertiary amine is 436 nm, It is preferable to have absorption at at least one wavelength among electromagnetic waves having wavelengths of 405 nm, 365 nm, and 248 nm.

As described above, a salt of a carboxylic acid, a carboxylic acid, and an amine that are photodecarboxylated contained in the photosensitive resin composition according to the present invention, particularly an aromatic component-containing carboxylic acid represented by the above formula (1). The salt of acid and amine functions as a photobase generator, so that a wide variety of polymer precursors can be applied, and the polymer obtained finally is not limited by the pattern formation process. A wide range of structures can be selected.
Moreover, according to this invention, a photobase generator can be adjusted and used by a simple method and using an inexpensive commercially available compound. In particular, since a compound belonging to the ketoprofen derivative represented by the formula (3) can be obtained at low cost, it is excellent in cost performance and the price as a photosensitive resin composition can be suppressed.
Furthermore, the photosensitive resin composition according to the present invention can be applied to a wider range of applications by applying a polyimide precursor or a polybenzoxazole precursor that has been applied to various applications as a polymer precursor. It can be used as a photosensitive polyimide resin composition or a photosensitive polybenzoxazole resin composition.
According to the present invention, a polyimide precursor or a polybenzoxazole precursor, which has conventionally had difficulty in obtaining a solubility contrast between an exposed area and an unexposed area, can be obtained without application of a dissolution inhibitor or a dissolution inhibitor. A pattern shape can be obtained.

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 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, Suitable for forming color filters, flexible display films, semiconductor devices, electronic components, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, other optical components, or building materials Yes.
In addition, a photosensitive polyimide precursor resin composition, which is one form of the polymer precursor resin composition, and a photosensitive polybenzoxazole precursor resin composition are polyimide or polybenzoxazole precursors having a wide range of structures. Therefore, the cured product obtained can be imparted with functions characteristic of polyimide and polybenzoxazole, such as heat resistance, dimensional stability, and insulation properties. It is suitable as a film, coating film or three-dimensional structure for all known members to which oxazole is applied.

FIG. 1 is a graph showing the relationship between the thermosetting temperature after ultraviolet irradiation of the photosensitive resin compositions of Examples and Comparative Examples and the polyimide precursor peak.

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.
Further, in the present invention, the electromagnetic wave causing the decarboxylation reaction of the salt of carboxylic acid and amine is not limited as long as it can cause the decarboxylation reaction, and not only the electromagnetic waves having wavelengths in the visible and invisible regions. , A particle beam such as an electron beam, and radiation or ionizing radiation collectively referring to electromagnetic waves and particle beams.

  The photosensitive resin composition according to the present invention is characterized by containing a salt of a carboxylic acid and an amine for photodecarboxylation and a polymer precursor.

  Ketoprofen, an aromatic component-containing carboxylic acid, has been reported to undergo a decarboxylation reaction via an intermediate such as a radical by absorption of electromagnetic waves according to the following reaction formula (Journal of Chemical Society., Faraday Trans. 1997, 93 (13), 2269-2275).

The present inventor has paid attention to the above decarboxylation reaction of ketoprofen. Although the salt of ketoprofen and amine is neutral, when ketoprofen is decarboxylated by absorbing electromagnetic waves, the salt cannot be formed and the amine is present alone, indicating basicity. On the other hand, the polyimide precursor can lower the temperature at which the imidization reaction is initiated by the catalytic action of the amine. In other words, the polyimide precursor is allowed to coexist with the salt of ketoprofen and amine, and by converting the salt to amine by irradiation with electromagnetic waves, the portion irradiated with electromagnetic waves can proceed to imidization at a lower temperature. it can.
In order to obtain a pattern using a photosensitive resin composition containing a salt of ketoprofen, an amine, and a polyimide precursor, imidization proceeds in a place where amine exists after irradiating electromagnetic waves to the place where the pattern is to be left. In a place where no amine is present, heating is performed at a temperature at which imidization does not proceed. As a result, imidization proceeds only in the place where the amine is present, that is, the place where the electromagnetic wave is irradiated, and the solubility is lowered. Therefore, the pattern is obtained by developing with a predetermined developer (organic solvent, aqueous alkali solution, etc.). be able to. Thereafter, depending on the purpose, it can be further heat-cured to form a polyimide pattern.

Based on the above findings, the inventors have found that the salt near the neutrality of the carboxylic acid and the amine cannot form a salt after decarboxylation and generates an amine, and the exposed amine is subjected to imidization using the generated amine as a catalyst. Was found to be able to impart a difference in solubility between the exposed and unexposed areas.
Accordingly, this salt not only promotes imidization but also acts as an effective photosensitive component for various polymer precursors or resin compositions.

Photosensitive polyimide precursor resin compositions using photobase generators have been known in the past, but there are many compounds with a special structure in which the molecular structure changes to amine through intramolecular transition by absorption of electromagnetic waves. Until now, there has been no proposal using a salt obtained by simply mixing a carboxylic acid to be decarboxylated and an amine.
In the present invention, a photosensitive resin composition can be prepared more easily and inexpensively by preparing and using a photobase generator by a simple technique and using an inexpensive commercially available compound. Moreover, the selection range of the polymer precursor which can be applied is wide, and it is widely applied in the field where the characteristics of the photosensitive polymer precursor resin composition and the cyclized product can be utilized. In particular, it is suitably applied in fields where the characteristics of the photosensitive polyimide precursor resin composition and its imidized product, which are typical examples thereof, can be utilized.

  As one of the salt of carboxylic acid and amine that undergoes photodecarboxylation, a salt of aromatic component-containing carboxylic acid and amine represented by the following formula (1) can be used.

(In the formula, R ^{1 to} R ⁵ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. R ⁶ and R ⁷ are each independently hydrogen or a monovalent organic group, and they may be the same or different, and the two may be the same as each other. R ^{8 to} R ¹⁰ may be independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. Also, two or more of them may be combined to form a cyclic structure.)

  More specifically, the aromatic component-containing carboxylic acid constituting the salt represented by the above formula (1) is a phenylacetic acid derivative, in which a carboxyl group and an aromatic ring are linked by methylene. A substituent may be introduced into the aromatic ring. The introduced substituents are monovalent organic groups, and these substituents may be linked to each other. In addition, one or more monovalent organic groups or divalent organic groups may be introduced into the portion of the methylene moiety to which hydrogen is bonded.

In R ^{1 to} R ⁵ of the aromatic component-containing carboxylic acid constituting the salt represented by the formula (1), a hydrogen atom and / or a substituent other than a hydrogen atom may be introduced at these positions.
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 and the like.
In addition, examples of other monovalent organic groups include groups having a hydrocarbon skeleton, which may contain a bond or substituent other than a hydrocarbon group such as a heteroatom. Examples of the group having such a hydrocarbon skeleton include a saturated or unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated group. Alkyl groups, aromatic groups such as phenyl and naphthyl, allyl groups, and halogen atoms, hydroxyl groups, mercapto groups, primary amino groups, secondary amino groups, tertiary groups on a saturated or unsaturated hydrocarbon skeleton Examples include various groups formed by bonding heteroatoms or groups containing heteroatoms such as amino, cyano, silyl, silanol, alkoxy, nitro, carboxyl, acetyl, acetoxy, and sulfone groups. It is done.

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. As an example in which they are connected, an aromatic ring is a polycyclic condensed aromatic ring such as a naphthalene ring, an anthracene ring, a pyridine ring, a furan ring, a thioxanthone ring, a heteroaromatic ring, an aromatic ring and a non-aromatic ring Examples thereof include polycyclic condensed rings containing.

Furthermore, a substituent represented by the following formula (2) may be introduced on the aromatic ring as the substituents R ^{1 to} R ⁵ . In particular, ketoprofen which is a commercially available compound or a derivative thereof, a compound in which a substituent represented by the following formula (2) is introduced into R ² is preferable from the viewpoint of cost and availability.

(In the formula, R ^{11 to} R ¹⁵ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. It may be bonded to form a ring structure.)

Examples of the monovalent organic group that can be introduced on the aromatic ring as the substituents R ^{11 to} R ¹⁵ include, for example, 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 and the like.
In addition, examples of other monovalent organic groups include groups having a hydrocarbon skeleton, which may contain a bond or substituent other than a hydrocarbon group such as a heteroatom. Examples of the group having such a hydrocarbon skeleton include a saturated or unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated group. Alkyl groups, aromatic groups such as phenyl and naphthyl, allyl groups, and halogen atoms, hydroxyl groups, mercapto groups, primary amino groups, secondary amino groups, tertiary groups on a saturated or unsaturated hydrocarbon skeleton Examples include various groups formed by bonding heteroatoms or groups containing heteroatoms such as amino, cyano, silyl, silanol, alkoxy, nitro, carboxyl, acetyl, acetoxy, and sulfone groups. It is done.
R ^{11 to} R ¹⁵ may be the same as or different from each other. Two or three or more groups out of R ^{11 to} R ¹⁵ may be bonded to each other to form a cyclic structure.

A hydrogen atom and / or a substituent other than a hydrogen atom may be introduced at the positions of R ⁶ and R ^{7 in} the salt of an aromatic component-containing carboxylic acid represented by formula (1) and an amine. R ⁶ and R ⁷ may be the same as or different from each other. R ⁶ and R ⁷ may be bonded to each other to form a cyclic structure.

By introducing a hydrogen atom or a substituent other than a hydrogen atom at positions R ⁶ and R ^7, the ease of decarboxylation can be adjusted. From this viewpoint, examples of the monovalent organic group that can be introduced at the positions of R ⁶ and R ⁷ include, in addition to a hydrogen atom, for example, a saturated or unsaturated alkyl group, a saturated or unsaturated alkyl halide group, or phenyl And groups having a hydrocarbon skeleton such as an aromatic group such as naphthyl and an allyl group. These substituents may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the substituent, and particularly have about 1 to 20 carbon atoms, preferably about 1 to 8 carbon atoms. Is preferred. These may be linear, branched or cyclic.
As a bond other than a hydrocarbon group such as a hetero atom contained in a group having a hydrocarbon skeleton, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, etc. Halogen atom, hydroxyl group, mercapto group, primary amino group, secondary amino group, tertiary amino group, cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, An unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group and the like can be mentioned, but are not particularly limited.

Furthermore, the monovalent organic group that can be introduced at the positions of R ⁶ and R ⁷ includes a halogen atom, a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a tertiary amino group, as long as the properties are not impaired. Using cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, unsaturated alkyl ether group, aryl ether group, unsaturated alkyl thioether group, aryl thioether group, etc. Also good. These may be linear, branched or cyclic.

A hydrogen atom and / or a substituent other than a hydrogen atom is introduced at the positions of R ^{8 to} R ¹⁰ of the amine that forms a salt of the aromatic component-containing carboxylic acid represented by formula (1) and the amine. May be. By introducing substituents at the positions of R ^{8 to} R ¹⁰ , the thermophysical properties and basicity of amines are different. The amine having a higher basicity has a stronger catalytic action for a dehydration condensation reaction such as imidization, and the dehydration condensation reaction at a lower temperature is possible with a smaller amount of addition. Therefore, the amine is preferably a secondary or higher amine, and more preferably a tertiary amine. In addition, an aliphatic amine such as triethylamine or an aromatic amine such as pyridine may be used as long as the object of the present invention is not impaired. However, from the viewpoint of using a highly basic amine, an aliphatic amine should be used. It is preferable to use an aliphatic secondary or tertiary amine, and it is particularly preferable to use an aliphatic tertiary amine.

  Moreover, it is preferable that an amine is not decomposed | disassembled in the temperature of the heating (the polymer is a polyimide precursor, the temperature of imidation) performed after exposure with respect to the coating film of the photosensitive resin composition of this invention. Specifically, it is preferable that the temperature (5% weight reduction temperature) when the amine is heated to reduce 5% weight from the initial weight is 100 ° C. or more. Furthermore, when the photosensitive resin composition of the present invention is used as a product, it is preferable that no impurities remain in the photosensitive resin composition. Therefore, a heating process performed after development (when the polymer is a polyimide precursor) , An amine that decomposes or volatilizes in the imidization process). Specifically, the temperature (50% weight reduction temperature) when the amine is heated and 50% weight is reduced from the initial weight is preferably 400 ° C. or less.

From this viewpoint, examples of the monovalent organic group that can be introduced at the positions of R ^{8 to} R ¹⁰ include, in addition to a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or phenyl. And groups having a hydrocarbon skeleton such as an aromatic group such as naphthyl and an allyl group. These substituents may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the substituent, and particularly have about 1 to 20 carbon atoms, preferably about 1 to 8 carbon atoms. Is preferred. These may be linear, branched or cyclic. Also, two or more of R ^{8 to} R ¹⁰ may be connected to form a ring.
As a bond other than a hydrocarbon group such as a hetero atom contained in a group having a hydrocarbon skeleton, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, etc. Halogen atom, hydroxyl group, mercapto group, primary amino group, secondary amino group, tertiary amino group, cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, An unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group and the like can be mentioned, but are not particularly limited.

Furthermore, as a monovalent organic group that can be introduced at the positions of R ^{8 to} R ¹⁰ , a halogen atom, a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a tertiary amino group, a cyano, as long as the characteristics are not impaired. Groups, silyl groups, silanol groups, alkoxy groups, nitro groups, carboxyl groups, acetyl groups, acetoxy groups, sulfone groups, unsaturated alkyl ether groups, aryl ether groups, unsaturated alkyl thioether groups, aryl thioether groups, etc. good. These may be linear, branched, or cyclic, and two or more of R ^{8 to} R ¹⁰ may be connected to form a ring.

In the present invention, a compound having two or more amino groups in the molecule may be used. For example, in 1,4-diazabicyclo [2.2.2] octane having two amino groups, Two molecules of aromatic component-containing carboxylic acid are used to make a neutral salt for one molecule.
Examples of amines include primary amines such as n-butylamine, amylamine, hexylamine and octylamine, secondary amines such as diethylamine, dipropylamine, diisopropylamine and dibutylamine, trimethylamine, triethylamine and tripropylamine. , Tributylamine, triethylenediamine, aliphatic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane, aromatic tertiary amines such as dimethylaniline, and isoquinoline, pyridine, collidine, betapicoline Heterocyclic tertiary amine such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and other alkylene diamines, diethylenetriamine, etc. Triamine, other tetramine compounds include benzylamine.

Conversely, when two aromatic component-containing carboxylic acids are linked to form a compound having two carboxylic acids, one molecule of aromatic component carboxylic acid is applied to two monoamine molecules, To do.
The present invention is intended to be applied to a resin composition as a combination salt so that the carboxyl group and amino group of an aromatic component-containing carboxylic acid that undergoes a decarboxylation reaction by absorption of electromagnetic waves are equimolar. In such a range, a compound having any number of carboxyl groups and a compound having any number of amino groups can be used in combination.
Furthermore, they may not be single, and from the viewpoint of solubility in the matrix, a plurality of salts, and further a plurality of aromatic component-containing carboxylic acids and amines can be used in combination.

Further, the position one of the substituents R ¹ to R ¹⁰ in the molecule of the aromatic component containing carboxylic acids and amines, by introducing one or more substituents, it is possible to adjust the wavelength of the absorption light It is possible to absorb a desired wavelength by introducing a substituent.
In particular, the substituents R ^{1 to} R ⁵ on the aromatic ring can be introduced by selecting the type of substituent relatively freely from the viewpoint of adjusting the absorption wavelength.

  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 is a substance that itself is a polymer and finally becomes a polymer that exhibits desired physical properties by an intramolecular reaction such as an intramolecular ring closure reaction. Preferably, it means a unit that forms a repeating unit having a cyclic structure with elimination of water molecules and / or alcohol molecules in the intramolecular ring-closing reaction.
In the present invention, a polymer precursor that is finally converted into a final product by the action of a base is typically used. However, the polymer precursor can be used even if it does not change to a final product by the action of a base. For example, in the case where components other than the polymer precursor contained in the photosensitive resin composition exhibit the function under the action of the base, the polymer precursor itself is finally converted into the final product by the action of the base. Even if it does not do, when it sees as the whole photosensitive resin composition, target reaction will advance by the effect | action of a base.

  In the present invention, a polyimide precursor or a polybenzoxazole precursor is particularly preferably used. Any polyimide or polybenzoxazole precursor can be used as the polyimide precursor or polybenzoxazole precursor, and a mixture of two or more separately synthesized polymer precursors may be used. .

  When using a polymer precursor whose thermosetting temperature is lowered by the catalytic action of a base, such as a polyimide precursor or a polybenzoxazole precursor, first, such a polymer precursor and photodecarboxylation are performed. An electromagnetic wave is irradiated to the part of the resin composition film or the molded product where the pattern on the molded body in which the salt of carboxylic acid and amine is combined is desired to remain. Then, an amine base is generated in the irradiated portion, and the thermosetting temperature of that portion is selectively lowered. Next, while the irradiated portion is thermally cured, the non-irradiated portion is heated at a processing temperature that is not thermally cured, and only the irradiated portion is cured. Next, a non-irradiated portion is dissolved with a predetermined developer (such as an organic solvent or an alkaline aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. A desired resin pattern is obtained by the above process.

  If a polyimide precursor or polybenzoxazole precursor that is soluble in an alkali solution is used, the solubility contrast between the exposed portion and the non-exposed portion during alkali development 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 copolymer of an aromatic acid component and an aromatic amine component,
Alternatively, a polyimide precursor obtained by 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, 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-hexafulpropane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-propane dianhydride, 2,3,6,7 -Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,4,9, 0 Bae Li Ren dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, and the like. 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. Examples of 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.

(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 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 synthesize | combining the aromatic component containing carboxylic acid and amine salt and polyimide precursor which are used by this invention is illustrated more concretely from this, this invention is not limited to this.
The salt of an aromatic component-containing carboxylic acid and amine can be obtained, for example, by mixing ketoprofen and 1,4-diazabicyclo [2.2.2] octane. To 1,4-diazabicyclo [2.2.2] octane and 2 moles of ketoprofen, gradually dehydrated cyclohexane is added while warming to 40 ° C. to 50 ° C. and completely dissolved. When it is cooled to 5 ° C., white precipitates that precipitate are collected to obtain the desired product.

  The aromatic component-containing carboxylic acid and amine salt of the present invention thus obtained has an absorption with respect to at least a part of the exposure wavelength in order to sufficiently exhibit the function of generating a photobase for imidization. There is a need. 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 aromatic component-containing carboxylic acid and amine salt preferably absorbs at least one of electromagnetic waves having wavelengths of 436 nm, 405 nm, 365 nm, and 248 nm.

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 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 of the exposure wavelength when the film thickness is 1 μm. It preferably exhibits a transmittance, and more preferably exhibits a transmittance 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.
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%, and still more 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 3,000 to 500,000. 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 is performed to obtain polyimide. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases and the solubility 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 an aromatic component-containing carboxylic acid and an amine salt, a polyimide precursor, and only a solvent, and further, a light or thermosetting component, A photosensitive resin composition may be prepared by blending a non-polymerizable binder resin other than the polyimide precursor 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-chloropropane Halogenated hydrocarbons such as 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; 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 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 benzyl dimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like Monoacylphosphine oxides or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones.

In the photosensitive resin composition of the present invention, as a supplementary role of the photosensitive compound having a salt of an aromatic component-containing carboxylic acid and an amine, other photosensitive components that generate an acid or a base by light may be added. good.
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. 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 salt of carboxylic acid and amine to be decarboxylated is usually 0.1 to 95% by weight based on the solid content of the polymer precursor contained in the photosensitive resin composition. , Preferably in the range of 0.5 to 60% by weight. If it is less than 0.1% by weight, it is difficult to obtain the effect of addition, and if it exceeds 95% by weight, it is difficult to satisfy various physical properties required for the finally obtained resin cured product.
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. 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. 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 some support and exposed to a predetermined pattern using light such as electromagnetic waves, photodecarboxylation that is a constituent of a salt of carboxylic acid and amine in the exposed portion Carboxylic acid undergoes decarboxylation to produce an amine. Accordingly, the salt of carboxylic acid and amine functions as a photobase generator, and imidizes the polyimide precursor in the exposed area.

The coating film of the photosensitive resin composition according to the present invention is preferably subjected to a heat treatment between the exposure process and the development process. This is preferably performed at a temperature at which the imidization rate differs between the site where the base is present and the site where the base is not present due to the action of the base generated by the irradiation of the electromagnetic wave, and a preferable heat treatment temperature. The range is usually about 60 ° C to 180 ° C.
When the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to create a difference in the imidization ratio between the exposed portion and the unexposed portion under realistic process conditions. On the other hand, when the heat treatment temperature is 180 ° C. or higher, the aromatic component-containing carboxylic acid and the amine salt are thermally decomposed, or imidation proceeds even in an unexposed portion where no amine exists, Difficult differences in solubility in unexposed areas.
This heat treatment may be any method as long as it is a publicly known method, and specific examples thereof include air, a circulation oven in a nitrogen atmosphere, heating with a hot plate, and the like, but are not particularly limited.

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 preferably exhibits a glass transition temperature of about 120 ° C. to 450 ° C., more preferably 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, the photosensitive resin composition according to the present invention includes a salt of a carboxylic acid, a carboxylic acid and an amine that are photodecarboxylated, in particular, an aromatic component-containing carboxylic acid represented by the above formula (1). As the salt of amine and amine functions as a photobase generator, a wide variety of polymer precursors can be applied, and the structure of the polymer finally obtained is not limited by the pattern formation process Can be selected from a wide range.
Moreover, according to this invention, a photobase generator can be adjusted and used by a simple method and using an inexpensive commercially available compound. In particular, since a compound belonging to the ketoprofen derivative represented by the formula (3) can be obtained at low cost, it is excellent in cost performance and the price as a photosensitive resin composition can be suppressed.

  The photosensitive resin composition according to the present invention is a known resin material such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical member. Can be used in all fields and products.

  The photosensitive resin composition according to the present invention has a wide range of fields and products in which properties such as heat resistance, dimensional stability, and insulation are effective, such as paints, printing inks, or color filters. Films for flexible displays, semiconductor devices, electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, holograms, optical members, or building materials, and are preferably used as the present invention. Printed material, color filter, flexible display film, semiconductor device, electronic component, interlayer insulating film, wiring coating film, optical circuit, light, at least partly formed of the photosensitive resin composition according to the invention or a thermosetting product thereof Articles of any of circuit components, antireflection films, holograms, optical members or building materials are provided.

  In particular, a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is mainly used as a pattern forming material (resist), and the pattern formed thereby is a permanent film made of polyimide or polybenzoxazole. Functions as a component that imparts heat resistance and insulation as, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, It is suitable for forming other optical members or electronic members.

(Production Example 1)
Ketoprofen (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.09 g (20 mmol) and 1,4-diazabicyclo [2.2.2] octane (manufactured by Kanto Chemical) 1.12 g (10 mmol) are placed in a 500 ml flask and placed in a 50 ° C. water bath. While heating at 0, cyclohexane was gradually added until ketoprofen and 1,4-diazabicyclo [2.2.2] octane were completely dissolved. Then, the white precipitation which precipitates when it cools was taken out, and 5.98g of the target photosensitive substances 1 represented by following formula (6) were obtained.

(Production Example 2)
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 the polyimide precursor 1 and 200 mg of the photosensitive material 1 were dissolved in 3 ml of NMP to obtain a photosensitive resin composition (photosensitive resin composition 1) of the present invention.

(Comparative Example 1)
Only 400 mg of the polyimide precursor 1 was dissolved in 3 ml of NMP to obtain a photosensitive resin composition (photosensitive resin composition 2) of a comparative example.

<Test>
(1) Thermosetting temperature The photosensitive resin composition 1 (Example 1) and the photosensitive resin composition 2 (Comparative Example 1) were each spin-coated on a chromium-plated glass plate so as to have a final film thickness of 2 μm. And dried on a hot plate at 80 ° C. for 30 minutes. Thereto, 10J ultraviolet irradiation was performed in terms of h rays with a manual exposure device (MA-1200, manufactured by Dainippon Screen Co., Ltd.). The infrared spectroscopic spectrum of this coating film was measured using IR-610 manufactured by JASCO Corporation and HOTPLATE EC-1200 manufactured by ASONE Co., Ltd. while heating from room temperature at 5 ° C./min to 350 ° C.
The spectrum derived from the precursor disappeared with heating, and a peak derived from polyimide generated by heating appeared. In order to confirm the progress of imidization, when the peak area of 1663 cm ⁻¹ derived from the precursor before the measurement was taken as 1, the amount of decrease in the peak area during the heating process was plotted.
The result is as shown in FIG. In the photosensitive resin composition 1, the decrease in the precursor occurred at a lower temperature than that in the photosensitive resin composition 2, and it was found that the difference in the imidization ratio between the two samples was maximized around 175 ° C.

(2) Pattern formation The photosensitive resin composition 1 (Example 1) was spin-coated on a glass plate so as to have a final film thickness of 2 μm, and dried on a hot plate at 80 ° C. for 30 minutes. Thereto, 10J ultraviolet irradiation was performed in terms of h-line in 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, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 350 ° C. for 1 hour to perform imidization.
From this result, it became clear that the photosensitive resin composition of the present invention can form a good pattern.

Claims (6)

It contains a salt of an aromatic component-containing carboxylic acid represented by the following formula (1) and a tertiary amine that undergoes photodecarboxylation and a polymer precursor, and the polymer precursor itself is a polymer. A photosensitive resin composition, which is a polymer precursor that finally becomes a polymer exhibiting the desired physical properties by an intramolecular reaction by the action of a base .
(In the formula, R ^{1 to} R ⁵ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. R ⁶ and R ⁷ are each independently hydrogen or a monovalent organic group, and they may be the same or different, and the two may be the same as each other. R ^{8 to} R ¹⁰ are each independently a monovalent organic group, and two or more of them may be the same or different from each other, and may be bonded to form a cyclic structure. Two or more of them may be combined to form a cyclic structure.) At least one of R ^{1 to} R ⁵ of the aromatic component-containing carboxylic acid constituting the salt of the aromatic component-containing carboxylic acid represented by the formula (1) and the tertiary amine is represented by the following formula (2). The photosensitive resin composition according to claim 1 .
(In the formula, R ^{11 to} R ¹⁵ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. It may be bonded to form a ring structure.) Aromatics-containing carboxylic acid constituting the salt of an aromatic component containing carboxylic acid and a tertiary amine represented by the formula (1) is, according to claim 1 or ketoprofen derivative represented by the following formula (3) 2. The photosensitive resin composition according to 2.
(In the formula, R ^{16 to} R ²⁴ are each independently a hydrogen atom or a monovalent organic group, and two or more of them may be the same or all may be different. R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a straight chain, branched or cyclic hydrocarbon group, and they may be the same or different. In addition, they may be bonded to each other to form a cyclic structure.) The photosensitive resin composition according to any one of claims 1 to 3 amine used in the salt of a carboxylic acid and a tertiary amine to the light decarboxylation is an aliphatic tertiary amine. Salts with the aromatics-containing carboxylic acid and a tertiary amine, 436nm, 405nm, 365nm, any one of claims 1 to 4, characterized in that it has an absorption in at least one wavelength of the electromagnetic wave with a wavelength of 248nm The photosensitive resin composition as described in 2. The photosensitive resin composition according to any one of claims 1 to 5 wherein the polymer precursor is soluble in an alkaline solution.