JP4978137B2 - 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. 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 polyimide or polybenzoxazole precursor resin composition that 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 like The present invention relates to an article produced using a 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 the method of processing the precursor. 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 a method of patterning by exposure and development in the state of a polyimide precursor, and then imidizing by heat treatment or the like to obtain a polyimide pattern, and the other is a polyimide itself that is not photosensitive itself. A pattern is formed by decomposing or elution by forming a resist pattern on the top with an organic substance, metal, etc., and treating the opening with a solution of hydrazine, inorganic alkali, organic alkali, etc., an organic polar solvent, or a mixture thereof. How to get.
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 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) 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 dihydropyridine 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 exposed. The dissolution rate of the part was also fast, and there was 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.
Furthermore, conventionally used photoacid (base) generators are expensive, and there is a problem that if the amount added is increased to increase the solubility contrast, the cost increases.

  The present invention has been made in view of the above circumstances, and the object thereof is to obtain a large solubility contrast regardless of the type of the polymer 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.

It contains an ammonium compound salt that decomposes by absorbing electromagnetic waves and desorbs a lower molecular amine than the original compound, and a polymer precursor, and the ammonium compound salt is an ammonium salt represented by the following formula (1). There, the polymer precursor is a polyimide precursor or a polybenzoxazole precursor der photosensitive resin composition characterized Rukoto.

(Wherein R ⁵ Carbon and R ⁶ The carbon to which is attached is directly bonded. R ¹ ~ R ⁴ And R ⁷ ~ R ¹⁰ Are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different from each other. Two or more of them may be combined to form a ring structure. R ¹¹ ~ R ¹³ Are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different. Two or more of them may be combined to form a ring structure. R ¹⁴ Is hydrogen or a monovalent organic group. A is a compound or element that can be an anion. )

  Ammonium compound salts that decompose by absorption of electromagnetic waves and desorb amines with lower molecular weight than the original compounds generate amine bases when irradiated with electromagnetic waves, so that polymer precursors that change into final products by the action of amine bases. It acts as a very effective photosensitive component on the body, for example a polyimide precursor.
  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 this, the said ammonium compound salt is effective as a photosensitive component.

The ammonium salt represented by the above formula (1) generates an amine base when irradiated with electromagnetic waves. Therefore, this ammonium salt is applied to a composition containing a polymer precursor that catalyzes a reaction in which a base is converted into a final product, such as a polyimide precursor, or a system in which a target reaction proceeds by the action of a base. On the other hand, it acts as a very effective photosensitive component.

The amine produced by the decomposition reaction after the ammonium salt absorbs electromagnetic waves is preferably a tertiary amine or an aliphatic amine, particularly an aliphatic tertiary amine, from the viewpoint of generating a highly basic amine. It is preferable.
Since the atoms bonded to the ammonium nitrogen of R ^{11 to} R ¹³ of the ammonium salt represented by the above formula (1) are all saturated carbon, the above-described aliphatic tertiary amine can be generated. Is particularly preferred.

  Since the wavelength of a high-pressure mercury lamp, which is a general exposure light source, is 436 nm, 405 nm, and 365 nm, the salt represented by the above formula (1) is at least one wavelength among electromagnetic waves having wavelengths of 436 nm, 405 nm, and 365 nm. In addition, since the wavelength in a KrF laser generally used for semiconductor production is 248 nm, it is preferable to have absorption at 248 nm.

As described above, an ammonium compound salt that decomposes by absorption of electromagnetic waves contained in the photosensitive resin composition according to the present invention and desorbs a lower molecular amine than the original compound, particularly in the above formula (1) The benzhydrylammonium salt represented can function as a photobase generator, so that a wide variety of polymer precursors can be applied, and the high yield finally obtained without being limited by the patterning process. The molecular structure can be selected from a wide range.
Moreover, since the benzhydryl ammonium salt according to the present invention is easy to synthesize and the raw materials can be obtained at a relatively 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 uses by applying a polyimide precursor or a polybenzoxazole precursor that has been applied to various uses as a polymer precursor. It can be used as a photosensitive polyimide composition or a photosensitive polybenzoxazole composition.
According to the present invention, a polyimide precursor or a polybenzoxazole precursor that has conventionally had difficulty in obtaining a solubility contrast between an exposed portion and an unexposed portion can be obtained without application of dissolution inhibitor and 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 made of polyimide. Suitable for forming color filters, flexible display films, semiconductor devices, electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, other optical members or electronic members, for example ing.
In addition, the photosensitive polyimide precursor resin composition, which is one form of the polymer precursor resin composition, and the photosensitive polybenzoxazole precursor resin composition are polyimide or polybenzoxazole precursors having a wide structure. 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.

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 and / or methacrylate may be used.
Further, in the present invention, the electromagnetic wave that causes the decomposition of the ammonium compound salt may be anything that can cause the decomposition reaction, and not only the electromagnetic waves having wavelengths in the visible and invisible regions, but also the electron beam. The particle beam, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams are included.

  The photosensitive resin composition according to the present invention is characterized by containing an ammonium compound salt capable of decomposing by absorption of electromagnetic waves and desorbing a lower molecular amine than the original compound, and a polymer precursor.

  Trimethylbenzhydrylammonium iodide, which is one of benzhydrylammonium salts, has been reported to cause a decomposition reaction by absorption of electromagnetic waves according to the following reaction formula (2) (Chemistry of Materials. 2002, 14). 918-923).

The present inventor has paid attention to the above decomposition reaction of trimethylbenzhydrylammonium iodide. Although trimethylbenzhydrylammonium iodide is a neutral salt, the elimination reaction of amine proceeds by absorbing electromagnetic waves and exhibits 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 coexists with the benzhydrylammonium salt, and by converting the salt to amine by irradiation with electromagnetic waves, the site irradiated with the electromagnetic waves reacts to the final product of the polyimide precursor. It is promoted and the imidization can proceed at a lower temperature.
In order to obtain a pattern using a photosensitive resin composition containing a benzhydrylammonium salt and a polyimide precursor, imidization proceeds in a place where an amine exists after irradiating an electromagnetic wave 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, where the electromagnetic wave is irradiated, and the solubility is lowered. Therefore, the pattern is developed by developing with a predetermined developer (organic solvent, alkaline aqueous solution, etc.). Obtainable. Then, according to the objective, it can heat further and can be set as a polyimide pattern.

Based on the above findings, the present inventors have found that an ammonium compound salt that is close to neutrality decomposes after absorbing electromagnetic waves and desorbs a lower molecular weight amine than the original ammonium compound salt, and the eliminated amine serves as an imide. It has been found that the exposed portion can be cured by carrying out the process to impart a difference in solubility between the exposed portion and the unexposed portion.
Therefore, 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, no one has been proposed that utilizes a salt that decomposes due to absorption of phosphine and releases an amine having a lower molecular weight than the original compound.
The present invention makes it possible to prepare a photosensitive resin composition more easily and inexpensively by using a photobase generator that can be synthesized by a simple technique and that can use an inexpensive commercially available compound as a raw material. it can. Moreover, the selection range of the applicable polymer precursor 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 a field where the characteristics of the photosensitive polyimide precursor resin composition, which is a typical example thereof, and the imidized product thereof can be utilized.
A benzhydryl ammonium salt represented by the following formula (1) can be used as one of the above ammonium compound salts that decompose by absorption of electromagnetic waves and desorb amines having a lower molecular weight than the original compound.

(In the formula, R ^{1 to} R ¹⁰ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or all may be different. The above may combine to form a cyclic structure, and R ^{11 to} R ¹³ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different. Two or more of them may be bonded to form a cyclic structure, R ¹⁴ is hydrogen or a monovalent organic group, and A is a compound or element that can be an anion. .)

The benzhydrylammonium salt contains a diphenylmethane skeleton, and has a bond between the methylene carbon of the diphenylmethane skeleton and the nitrogen of the amine. As a result, the benzhydrylammonium salt exists as a salt with a positive anion at the nitrogen site of the amine and a positive anion.
In this case, one or more monovalent organic groups may be introduced instead of hydrogen in the methylene moiety.

In R ^{1 to} R ¹⁰ of the benzhydrylammonium salt represented by the formula (1), a hydrogen atom and / or a monovalent 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 ¹⁰ include a halogen atom, a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, a tertiary amino group, and cyano. Groups, silyl groups, silanol groups, alkoxy groups, nitro groups, carboxyl groups, acetoxy groups, sulfone groups, and acyl groups such as acetyl groups and benzoyl groups.
Other monovalent organic groups include groups having a hydrocarbon skeleton, which may contain bonds or substituents other than hydrocarbon groups such as heteroatoms, which may be linear or branched. It may be annular. Examples of the group having 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 alkyl group, or , Aromatic groups such as phenyl and naphthyl groups, allyl groups, and further, halogen atoms, hydroxyl groups, mercapto groups, primary amino groups, secondary amino groups, tertiary amino groups on a saturated or unsaturated hydrocarbon skeleton , Cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, and other various substituents formed by bonding hetero atoms or groups containing hetero atoms. .

R ^{1 to} R ¹⁰ may be the same as or different from each other. Two or more groups of R ^{1 to} R ¹⁰ may be bonded to each other to form a cyclic structure.
For example, the aromatic ring is a polycyclic condensed aromatic group such as a naphthalene ring or an anthracene ring, a heteroaromatic ring such as a pyridine ring or a furan ring, an aromatic ring such as a thioxanthone ring, and a non-aromatic ring. The thing etc. which became a polycyclic fused ring containing these can be illustrated.
In addition, the carbon to which R ⁵ is bonded and the carbon to which R ⁶ are bonded may be directly bonded, and the diphenylmethane skeleton may be a fluorene skeleton.

As for the position of R ^{14 in} the benzhydrylammonium salt represented by the formula (1), a hydrogen atom or a substituent other than a hydrogen atom may be introduced at this position. By introducing a substituent at the position of R ^14, the ease of decomposition due to absorption of electromagnetic waves can be adjusted.
From this viewpoint, examples of the monovalent organic group that can be introduced at the position of R ¹⁴ include, in addition to a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated alkyl halide group, phenyl, naphthyl, and the like. And a group having a hydrocarbon skeleton such as an aromatic group or 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 carbon hydrogen 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 position of R ¹⁴ , 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, as long as the characteristics are not impaired. 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 and the like may be used. These may be linear, branched or cyclic.

As for the position of R ^{11 to} R ¹³ of the ammonium group forming the benzhydryl ammonium salt represented by the formula (1), a hydrogen atom and / or a substituent other than a hydrogen atom may be introduced at this position. . By introducing a substituent at the positions of R ^{11 to} R ¹³ , the thermal properties and basicity of the leaving amine are different.
Examples of amines with lower molecular weight than the original compound, which are eliminated by decomposition of benzhydrylammonium salt, are trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2]. Examples include octane, quinuclidine, and aliphatic tertiary amines such as 3-quinuclidinol, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as isoquinoline, pyridine, collidine, and betapicoline. It is done.

As the catalytic action for imidization, the greater the basicity, the greater the effect as a catalyst, and imidization at a lower temperature is possible with a smaller amount of addition. In general, secondary amines are more basic than primary amines, and tertiary amines are more basic than secondary amines, and their catalytic effect is greater. Therefore, the amine produced after decomposition of the benzhydrylammonium salt according to the present invention 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 generated 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 may be generated. An amine is preferably generated, an aliphatic secondary or tertiary amine is more preferably generated, and an aliphatic tertiary amine is particularly preferably generated.
When the atoms bonded to the ammonium nitrogen of R ^{11 to} R ¹³ of the benzhydryl ammonium salt represented by the above formula (1) are all saturated carbons, that is, carbon atoms having SP3 orbitals, Is particularly preferable from the viewpoint of using an amine having a high basicity as described above.

  The benzhydrylammonium salt may not be decomposed at the heating temperature (imidation temperature when the polymer is a polyimide precursor) after exposure to the coating film of the photosensitive resin composition of the present invention. preferable. Specifically, it is preferable that the temperature (5% weight reduction temperature) when the benzhydryl ammonium salt 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) , Which are decomposed or volatilized in the imidization process). Specifically, the temperature when the 50% weight is reduced from the initial weight (50% weight reduction temperature) is preferably 400 ° C. or less.

From this viewpoint, examples of the monovalent organic group that can be introduced at the positions of R ^{11 to} R ¹³ include a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or an aromatic group such as phenyl and naphthyl, Examples include groups having a hydrocarbon skeleton such as an allyl group. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group, 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, and R ^{11 to} R ¹³ may be linked to form a cyclic shape.
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 ^{11 to} R ¹³ , 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 R ^{11 to} R ¹³ may be linked to form a cyclic shape.

Moreover, in this invention, you may use the ammonium compound salt which has an ammonium group in two or more places in one molecule | numerator.
As an example, a diamine compound such as 1,4-diazabicyclo [2.2.2] octane having two amino groups per molecule is used, and benzhydryl ammonium is used for one molecule of such a diamine compound. Examples are those which are almost neutral salts using two molecules of the diphenylmethane skeleton component constituting the derivative. From such a salt, an amine having two amino groups in one molecule such as 1,4-diazabicyclo [2.2.2] octane is eliminated.

Another example is a salt formed by using two molecules of monoamine in a compound having two or more neutralization points for amino groups per molecule. For example, a compound in which two diphenylmethane structures are connected to each other and two monoamines are used for one molecule of the diphenylmethane compound to form a substantially neutral salt is exemplified. Two molecules of monoamine are eliminated from such a salt.
That is, in both cases of the first example and the second example, a salt can be formed by making the number of methylene sites of the diphenylmethane skeleton component correspond to the number of nitrogen atoms of the amine and making the number the same. .
However, when the number of nitrogen atoms of the amine is small relative to the number of methylene moieties of the diphenylmethane skeleton, the present invention can be applied to the present invention, but the number of nitrogen atoms of the amine is smaller than the number of methylene moieties of the diphenylmethane skeleton component. If it is large, the salt becomes a basic compound, and imidation catalysis may develop even in the unexposed area, and the solubility contrast in the exposed and unexposed areas becomes small.

  The purpose of the present invention is to apply to the resin composition a salt that decomposes by absorption of electromagnetic waves and produces an amine, and within a range not contrary to this, any number of compounds having any number of diphenylmethane skeleton components and any number These compounds having an amino group can be used in combination. Furthermore, they do not have to be single, and a plurality of salts can be used in combination from the viewpoint of solubility in the matrix.

A in the formula (1) is a compound or element that can be an anion. Specifically, halide ions, hydroxide ions, carbonate ions, bicarbonate ions, aliphatic and aromatic carboxy ions, aliphatic and aromatic sulfoxy ions, and their halides, hexafluoride Examples include antimonate ions (SbF ₆ ⁻ ) and phosphorus hexafluoride ions (PF ₆ ⁻ ).

Moreover, it is possible to adjust the wavelength of light to be absorbed by introducing one or more substituents into the substituents R ^{1 to} R ¹⁴ of the salt of the present invention. It is also possible to absorb the wavelength.
In particular, the substituents R ^{1 to} R ¹⁰ on the aromatic ring can introduce a substituent relatively freely from the viewpoint of improving sensitivity and adjusting the absorption wavelength. For example, the absorption wavelength can be shifted to a higher wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.

  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 method for synthesizing the benzhydrylammonium salt according to the present invention is illustrated more specifically, but the present invention is not limited thereto. The benzhydryl ammonium salt according to the present invention can be synthesized by a plurality of synthesis routes.
The benzhydrylammonium salt can be synthesized, for example, by reacting aminodiphenylmethane and iodomethane. The target product can be obtained by dissolving aminodiphenylmethane and 24 equivalents of iodomethane in methanol in the presence of an inorganic base such as sodium carbonate and boiling. For example, it can be synthesized by reacting 9-bromofluorene with quinuclidine. The desired product can be obtained by stirring 9-bromofluorene and quinuclidine in an inert gas atmosphere in a toluene solvent at room temperature for 15 hours and filtering the precipitated salt.

The benzhydrylammonium salt thus obtained needs to have absorption for at least a part of the exposure wavelength in order to sufficiently exhibit the function of generating a photobase for imidization. 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 benzhydrylammonium salt preferably absorbs electromagnetic waves having at least one wavelength among electromagnetic waves having wavelengths of at least 436 nm, 405 nm, 365 nm, and 248 nm.
Note that the benzhydrylammonium salt has absorption at the above-mentioned wavelength means that the benzhydrylammonium salt is 1 × 10 ⁻⁴ mol / L or less in a solvent that does not absorb in the measurement region (for example, acetonitrile). Dissolve at a concentration (usually about 1 × 10 ⁻⁴ mol / L to about 1 × 10 ⁻⁵ mol / L) and measure the absorbance with an ultraviolet-visible spectrophotometer (for example, UV-2550 (manufactured by Shimadzu Corporation)). This can be clarified. If the absorption of benzhydrylammonium salt is strong, the measurement concentration is appropriately reduced.

The polymer precursor used in the photosensitive resin composition of the present invention refers to a substance that itself is a polymer and becomes a polymer that finally shows the desired physical properties by an intramolecular ring-closing reaction, preferably In the intramolecular ring-closing reaction, it means that a repeating unit having a cyclic structure is formed with elimination of water molecules and / or alcohol molecules.
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, when a component other than the polymer precursor contained in the photosensitive resin composition exerts its function by receiving the action of a base, the polymer precursor is finally converted into a final product by the action of the base. Even if it is not a thing, when it sees as the whole photosensitive resin composition, the 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. As a polyimide precursor and a polybenzoxazole precursor, any polyimide precursor or polyoxazole precursor may be used depending on its mechanism, or a mixture of two or more separately synthesized polymer precursors may be used.

  When using a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor whose thermosetting temperature is lowered by the catalytic action of a base, first, such a polymer precursor and a benzhydryl ammonium salt are used. Irradiate an electromagnetic wave to the portion of the resin composition coating film or the molded body where the pattern on the molded body 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, the irradiated portion is thermally cured, but 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 pattern is obtained by the above steps.

  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 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 an acid dianhydride with a monohydric alcohol, an amino compound, an epoxy compound, etc., and reacting a diamino compound or its derivative with a carboxylic acid of an ester acid or an amic acid monomer. 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-dicarboxyphenyl) 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-hexafluoropropane Anhydride, 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} propane dianhydride,

2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarbox ) 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- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetra Carboxylic dianhydride, 3,4,9,10 -Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic 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' -Diaminodiphenylmethane, 2,2 Di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-amino) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- ( 3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1, 1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenyl) Noxy) 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-ditrifluoromethylben) Di) 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-aminophenoxy) biphenyl Bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4- Aminophenoxy) phenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) Enoxy] 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, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) poly Methylsiloxane, 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 (3). 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 (3), 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.

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 addition, the polyamide alcohol that is a polybenzoxazole precursor used in the present invention is preferably a compound represented by the general formula (4), and the compound comprises a dicarboxylic acid derivative such as a dicarboxylic acid halide and dihydroxydiamine. It can be obtained by addition reaction in an organic solvent.

(In Formula (4), R ¹⁵ is a divalent organic group. R ¹⁶ is a tetravalent organic group.)
In addition, although the divalent value of R ¹⁵ indicates only the valence for bonding with an acid, it may have another substituent. Similarly, the tetravalent value of R ¹⁶ indicates only the valency for bonding with an amine and a hydroxyl group, but may have other substituents.

  Examples of the dicarboxylic acid and derivatives thereof used as necessary include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-benzophenone dicarboxylic acid, 3,4′-benzophenone dicarboxylic acid, 3,3′- Benzophenone dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 3,4′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4′-diphenyl ether dicarboxylic acid, 3 , 3′-diphenyl ether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 3,4′-diphenylsulfone dicarboxylic acid, 3,3′-diphenylsulfone dicarboxylic acid, 4,4′-hexafluoroisopropylidene dibenzoic acid 4,4'-dicarboxydiphenyla 1,4-phenylenediethanoic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,2-trifluoroethane, bis (4-carboxyphenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5 -Chloroisophthalic acid, 2,2-bis- (p-carboxyphenyl) propane, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 2,6-naphthalenedicarboxylic acid, or acid halides thereof, And active esters with hydroxybenzotriazole, etc. The present invention is not limited. These may be used alone or in combination of two or more.

  Specific examples of dihydroxydiamine include, for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2- Bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) Hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino- -Hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 3-diamino-4,6- Examples thereof include, but are not limited to, dihydroxybenzene. These may be used alone or in combination of two or more.

Polymer precursors such as polyimide precursors and polybenzoxazole precursors have a film thickness of 1 μm in order to increase the sensitivity of the photosensitive resin composition and obtain a pattern shape that accurately reproduces the mask pattern. Furthermore, it is preferable that the transmittance is at least 5% or more with respect to the exposure wavelength, and it is more preferable that the transmittance is 15% or more.
The high transmittance of the polymer precursor such as the polybenzoxazole precursor with respect to the exposure wavelength means that the loss of light is small, 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 formed, it is preferably 5% or more, more preferably 15%, and still more preferably 50% or more.
When exposure is performed with a KrF laser having a wavelength of 248 nm, the transmittance at 248 nm is preferably 5% or more, more preferably 15%, and even more preferably 50% or more when formed on a film having a thickness of 1 μm. .

The weight average molecular weight of a polymer precursor such as a polyimide precursor is preferably in the range of 3,000 to 1,000,000, and in the range of 5,000 to 500,000, depending on the application. More preferably, the range is from 10,000 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), may be the molecular weight of the polyimide precursor itself, or after chemical imidization treatment with acetic anhydride or the like. Things can be used.

The photosensitive resin composition according to the present invention may be a simple mixture of a polymer precursor such as a benzhydrylammonium salt and a polyimide precursor, and a solvent alone. 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-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-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-di Thioxanthones such as methylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylpyroxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine And monoacylphosphine oxides such as oxide or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones.

In 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 a benzhydryl ammonium salt.
Examples of the compound that generates an acid by light include photosensitive diazoquinone compounds having a 1,2-benzoquinone diazide or 1,2-naphthoquinone diazide structure. US Pat. Nos. 2,772,972, 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, 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 benzhydrylammonium salt represented by the formula (1) is usually 0.1 to 95 with respect to the solid content of the polyimide precursor contained in the photosensitive resin composition. It is contained in the range of 0.5% by weight, preferably 0.5 to 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 various physical properties required for the finally obtained cured resin.
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 coated on some support and exposed to a predetermined pattern using light such as electromagnetic waves, the benzhydrylammonium salt undergoes a decomposition reaction in the exposed portion, and the original A lower molecular amine than benzhydrylammonium salt is eliminated. Therefore, the benzhydrylammonium salt according to the present invention functions as a photobase generator and imidizes the polyimide precursor in the exposed portion.

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 and unexposed areas under realistic process conditions. On the other hand, when the heat treatment temperature is 180 ° C. or higher, the benzhydrylammonium salt is thermally decomposed, or imidation proceeds even in an unexposed portion where no amine is present, so that the exposed portion and the unexposed portion are dissolved. Difficult gender difference.
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. Here, the glass transition temperature in the present invention is tan δ (tan δ = loss elastic modulus (tan δ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape. It is obtained from the peak temperature of E ″) / storage elastic modulus (E ′)). The dynamic viscoelasticity measurement can be performed, for example, with a viscoelasticity measuring device Solid Analyzer RSA II (manufactured by Rheometric Scientific) at a frequency of 3 Hz and a temperature rising rate of 5 ° C./min. When the polyimide and polybenzoxazole obtained from the photosensitive resin composition cannot be formed into a film shape, the temperature is determined based on the inflection point of the baseline of the differential thermal analyzer (DSC).
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. Here, the linear thermal expansion coefficient in this invention can be calculated | required with the thermomechanical analyzer (TMA) of the film of the polyimide and polybenzoxazole obtained from the photosensitive resin composition obtained by this invention. Using a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku Corporation), the heating rate is 10 ° C./min, and the tensile load is 1 g / 25,000 μm ² so that the weight per cross-sectional area of the evaluation sample is the same. .

As described above, in the photosensitive resin composition according to the present invention, the benzhydrylammonium salt represented by the formula (1) functions as a photobase generator, so that a wide variety of polymer precursors can be obtained. The structure of the finally obtained polyimide can be selected from a wide range without being limited by the patterning process.
In addition, the aromatic component-containing and / or aliphatic component-containing halides and amines constituting the benzhydrylammonium salt can be obtained at low cost, 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 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. The photosensitive resin according to the present invention is suitably used as a material for forming semiconductor devices, electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, holograms, optical members or building materials. Printed matter, color filter, flexible display film, semiconductor device, electronic component, interlayer insulating film, wiring coating film, optical circuit, optical circuit component, antireflection, at least partly formed of the composition or its thermoset Articles of either 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)
Under an argon stream, 2.38 g (9.8 mmol) of 9-bromofluorene (manufactured by Tokyo Chemical Industry) was dissolved in 300 mL of dried toluene in a 1000 mL three-necked flask. Quinuclidine (manufactured by Aldrich) 1.20 g (10.8 mmol) was added thereto, and the mixture was stirred at 23 ° C. for 15 hours. The precipitate was filtered, and the filtrate was taken out to obtain 3.02 g of the intended photosensitive substance 1 represented by the following formula (5).
The photosensitive substance 1 is dissolved in acetonitrile at a concentration of 1 × 10 ⁻⁴ mol / L, a quartz cell (optical path length: 10 mm) is filled with the solution, and an ultraviolet-visible spectrophotometer (UV-2550 (manufactured by Shimadzu Corporation) is filled. )) To measure the absorbance.
As a result, the photosensitive material 1 had absorption at 254 nm.

(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.

(Production Example 3)
A 100 mL three-necked flask equipped with a reflux tube was purged with nitrogen, and then 25 mL of dehydrated benzene and 2.08 g (10 mmol) of 2-acetylfluorene were added and dissolved by stirring at room temperature. 1.78 g (10 mmol) of N-bromosuccinimide and 0.024 g (0.1 mmol) of benzoyl peroxide were added and heated under reflux for 17 hours. The solution was cooled, and the resulting precipitate was collected by filtration to give 2.37 g (8.1 mmol, 81% yield) of 2-acetyl 9-bromofluorene as a pale yellow solid.
Nitrogen-substituted 200 mL eggplant flask was charged with 0.718 g (2.5 mmol) of 2-acetyl 9-bromofluorene and 75 mL of dehydrated toluene, stirred for 5 minutes at room temperature, and then added with 0.278 g (2.5 mmol) of quinuclidine. And stirred at room temperature for 2 days. This solution is cooled, and the resulting precipitate is filtered. The filtrate is taken out and washed with cold toluene to obtain 0.8 g of the desired photosensitive substance 2 represented by the following formula (6). (2.0 mmol, 80% yield), obtained as a brown solid.
When the absorbance was measured in the same manner as in Production Example 1, the photosensitive material 2 had absorption at 254 nm and 365 nm.

(Production Example 4)
A 100 mL three-necked flask equipped with a reflux tube was purged with nitrogen, and then 25 mL of dehydrated benzene and 1.96 g (10 mmol) of 2-methoxyfluorene were added and dissolved by stirring at room temperature. 1.78 g (10 mmol) of N-bromosuccinimide and 0.024 g (0.1 mmol) of benzoyl peroxide were added and heated under reflux for 48 hours. The solution was cooled, and the resulting precipitate was collected by filtration to obtain 0.68 g (2.5 mmol, yield 25%) of 2-methoxy 9-bromofluorene as a pale yellow solid.
Nitrogen-substituted 200 mL eggplant flask was charged with 0.68 g (2.5 mmol) of 2-methoxy 9-bromofluorene and 75 mL of dehydrated toluene, stirred for 5 minutes at room temperature, and then added with 0.278 g (2.5 mmol) of quinuclidine. And stirred at room temperature for 2 days. This solution is cooled, and the resulting precipitate is filtered. The filtrate is taken out and washed with cold toluene to obtain 0.77 g of the desired photosensitive substance 3 represented by the following formula (7). (2.0 mmol, 80% yield), obtained as a brown solid.
When the absorbance was measured in the same manner as in Production Example 1, the photosensitive material 3 had absorption at 254 nm and 365 nm.

(Production Example 5)
A 100 mL three-necked flask equipped with a reflux tube was purged with nitrogen, and then 25 mL of dehydrated benzene and 2.70 g (10 mmol) of 2-phenoxyfluorene were added and stirred and dissolved at room temperature. 1.78 g (10 mmol) of N-bromosuccinimide and 0.024 g (0.1 mmol) of benzoyl peroxide were added and heated to reflux for 20 hours. The solution was cooled, and the resulting precipitate was collected by filtration to obtain 2.62 g (7.5 mmol, yield 75%) of 2-phenacyl 9-bromofluorene as a pale yellow solid.
To a 200 mL eggplant flask purged with nitrogen, add 0.87 g (2.5 mmol) of 2-phenacyl 9-bromofluorene and 75 mL of dehydrated toluene, and after stirring at room temperature for 5 minutes, add 0.278 g (2.5 mmol) of quinuclidine. And stirred at room temperature for 2 days. This solution is cooled, and the resulting precipitate is filtered. The filtrate is taken out and washed with cold toluene to obtain 1.01 g of the desired photosensitive substance 4 represented by the following formula (8). (2.2 mmol, 88% yield), obtained as a brown solid.
When the absorbance was measured in the same manner as in Production Example 1, the photosensitive material 4 had absorption at 254 nm and 365 nm.

Example 1
400 mg of the polyimide precursor 1 and 200 mg of the photosensitive substance 1 were dissolved in 3 mL of NMP to obtain the 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 comparative photosensitive resin composition 1.

(Example 2)
400 mg of the polyimide precursor 1 and 60 mg of the photosensitive substance 2 were dissolved in 3 mL of NMP to obtain the photosensitive resin composition 2 of the present invention.

Example 3
400 mg of the polyimide precursor 1 and 60 mg of the photosensitive material 3 were dissolved in 3 mL of NMP to obtain the photosensitive resin composition 3 of the present invention.

Example 4
400 mg of the polyimide precursor 1 and 60 mg of the photosensitive substance 4 were dissolved in 3 mL of NMP to obtain the photosensitive resin composition 4 of the present invention.

<Test>
(1) Thermosetting temperature The photosensitive resin composition 1 (Example 1) and the comparative photosensitive resin composition 1 (Comparative Example 1) were each spun on a chrome-plated glass so as to have a final film thickness of 2 μm. It was coated 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 (manufactured by ASONE, HOTPLATE EC-1200) 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, it was found that the decrease in the precursor occurred at a lower temperature than the comparative photosensitive resin composition 1, and the difference in the imidization ratio between the two samples was maximized around 160 ° C. .

(2) Pattern formation Each of the photosensitive resin compositions 1 to 4 (Examples 1 to 4) was spin-coated on glass 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 was revealed that the photosensitive resin composition of the present invention can form a good pattern.

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.

Claims (10)

It contains an ammonium compound salt that decomposes by absorbing electromagnetic waves and desorbs a lower molecular amine than the original compound, and a polymer precursor, and the ammonium compound salt is an ammonium salt represented by the following formula (1). There, the polymer precursor is a polyimide precursor or a polybenzoxazole precursor der photosensitive resin composition characterized Rukoto.

(In the formula, the carbon to which R ⁵ is bonded and the carbon to which R ⁶ are bonded are directly bonded. R ^{1 to} R ⁴ and R ^{7 to} R ¹⁰ are each independently hydrogen or a monovalent organic group, Two or more of them may be the same or different from each other, or two or more of them may be bonded to form a cyclic structure, and R ^{11 to} R ¹³ are independent of each other. These may be hydrogen or a monovalent organic group, and two or more of them may be the same or different, and two or more of them may combine to form a cyclic structure. R ¹⁴ is hydrogen or a monovalent organic group, and A is a compound or element that can be an anion.)   The photosensitive resin composition according to claim 1, wherein the polymer precursor is converted into a final product by the action of a base. The photosensitive resin composition according to claim 1 or 2 , wherein the amine that is eliminated when the benzhydrylammonium salt represented by the formula (1) is decomposed is a tertiary amine. The photosensitive resin composition according to any one of claims 1 to 3, wherein the amine eliminated when the benzhydrylammonium salt represented by the formula (1) is decomposed is an aliphatic amine. object. The photosensitive group according to any one of claims 1 to 4 , wherein atoms bonded to ammonium nitrogen of R ^{11 to} R ¹³ of the ammonium salt represented by the formula (1) are all saturated carbon. Resin composition. Ammonium salt represented by the formula (1) is, 436nm, 405nm, 365nm, according to any one of claims 1 to 5, characterized in that it has an absorption in at least one wavelength of the electromagnetic wave of the wavelength of 254nm Photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 6 wherein the polymer precursor is soluble in an alkaline solution. The photosensitive resin composition according to any one of claims 1 to 7 wherein the polyimide precursor is a polyamic acid. Paint or printing ink, or color filter, flexible display film, semiconductor device, 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 any one of claims 1 to 8 , which is used as a material. A printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, at least partly formed of the photosensitive resin composition according to any one of claims 1 to 9 or a cured product thereof. Article of any of wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material.

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