JP4816176B2 - Photosensitive resin composition, article, and negative pattern forming method - 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 for forming a pattern by increasing the contrast of the dissolution rate of the part with respect to the developer and then imidizing to obtain a polyimide pattern;
(B) The polyamic acid of the polyimide precursor is mixed with a compound such as a dihydropyridine derivative that becomes a basic substance by exposure to electromagnetic waves, and after exposure, the basic substance generated in the exposed portion is heated at an appropriate temperature. The solubility of the exposed area in the developer is improved by the action, and a positive pattern is formed by increasing the contrast of the dissolution rate between the exposed area and the unexposed area of the developer, and then completely imidized. Technique for obtaining a polyimide pattern (Patent Document 1);

(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 forming a pattern by reducing solubility and increasing the contrast of the dissolution rate of the exposed area and unexposed area to the developer, followed by imidization to obtain a polyimide pattern (Patent Document 2);
(D) The polyimide precursor polyamic acid and the compound having a radically polymerizable ethylenically unsaturated bond having a basic site are mixed to form an ion bond between the two, and the sensitizer is mixed therewith for exposure. A radical pair is formed in the part to reduce the solubility in the developer, and the pattern is formed by increasing the contrast of the dissolution rate in the developer between the exposed part and the unexposed part. (Patent document 3);
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 portion and unexposed portion with respect to the developer to form a pattern, then imidize to obtain a polyimide pattern,
(F) The polyisoimide of the polyimide precursor is mixed with o-nitrobenzyl carbamate as a photobase generator, and after the exposure, the isomerization from the polyisoimide to the polyimide is advanced by the action of the base generated by the exposure by heating. And a method of obtaining a pattern by increasing the contrast of the dissolution rate with respect to the organic solvent (Patent Document 4):
Etc. have 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 molecular skeleton having a high transmittance with respect to the exposure wavelength.

The technique shown in Patent Document 4 uses a polyisoimide that is soluble only in an organic solvent as a polyimide precursor, and development during pattern formation must be performed in an organic solvent such as cyclohexane. This Patent Document 4 relates to a polyisoimide as a polymer precursor, “in addition to the isoimide unit represented by the above (Chemical Formula 4), an imide unit is contained in a range of 60 mol% or less, and further 20 mol% or less. Note that the amic acid unit can also be contained in a range that does not cause a significant decrease in the residual film thickness ratio ”(paragraph 0018). A solvent or an inorganic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or an organic alkaline aqueous solution such as propylamine, butylamine, monoethanolamine, tetramethylammonium hydroxide, choline, or a mixture of two or more of them may be used. Is possible "(paragraph 0041).
If the polyisoimide contains a large amount of amic acid units, development with an alkaline aqueous solution may be possible. However, Patent Document 4 merely describes that an amic acid unit can be contained in a range that does not cause a significant decrease in the remaining film thickness ratio. According to this description, the content of the amic acid unit is extremely small. Since it is limited to the range, it is difficult to think that the content of the amic acid unit that allows development with an alkaline aqueous solution is allowed. Patent Document 4 does not describe a repeating unit capable of imparting alkaline aqueous solution developability other than an amic acid unit.

Moreover, in the Example of patent document 4, the example developed with alkaline aqueous solution does not exist. It is impossible to estimate the content of the amic acid unit in the polyisoimide only by the polyisoimide synthesis conditions described in the examples of Patent Document 4, and organic solvent development is performed in the examples. Further, the possibility of development with an aqueous alkali solution cannot be estimated.
That is, Patent Document 4 does not describe a polyisoimide that can be developed in an alkaline aqueous solution when combined with nitrobenzyl carbamate as a photobase generator, and a polyisoimide that can be developed in an alkaline aqueous solution when combined with the acyloxime ester. There is also no description of the means by which it is possible to obtain

  On the other hand, Patent Document 4 discloses, as a comparative example, an example in which a polyamic acid is used in place of polyisoimide, but the comparative example only performs organic solvent development. In addition, in the comparative example, a pattern can be formed as follows: “However, the exposed portion is partially dissolved together with the unexposed portion during development, and a good negative pattern cannot be obtained.” It states that it was unsuccessful. These descriptions alone cannot predict the developability with an alkaline aqueous solution when a photobase generator such as nitrobenzyl carbamate is used as a photobase generator in combination with a polyamic acid.

Originally, a photobase generator in which a neutral compound changes to basic by absorbing electromagnetic waves has been mainly applied to the photo-curing use of epoxy resins. Used for the purpose of improving solvent resistance, heat resistance, and surface hardness by ring-opening polymerization of an epoxy group by the action of a base generated from a photobase generator, resulting in an increase in molecular weight or a crosslinked structure. It is
For such purposes, various base generators have been proposed. The photocuring reaction of epoxy resin using oxime ester as a photobase generator has already been reported (Journal of Photopolymer Science and Technology Vol.15 2002 145-152).
The oxime ester is considered to be basic in its neutrality by the following reaction mechanism, and the covalent bond between nitrogen and oxygen at the oxime ester site is broken by the absorption of electromagnetic waves, A reaction mechanism for producing a primary amine with a decarboxylation reaction has been proposed.

  In recent years, there has been a need for a photosensitive resin composition that is capable of developing a basic aqueous solution and that is negatively sensitive and inexpensive because of environmental problems, waste liquid processing costs, and required physical properties as a permanent film. Yes. However, as described above, photosensitive resin compositions, particularly photosensitive polyimides, are mostly developed by organic solvent development, and there are limited photosensitive resin compositions that can be developed with basic aqueous solutions. There has been a demand for a photosensitive resin composition that can be developed in an aqueous solution.

Japanese Patent Laid-Open No. 6-43648 JP 61-293204 A Japanese Examined Patent Publication No.59-52822 JP-A-8-95246

  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition that can be developed with a basic aqueous solution using a polymer precursor that is soluble in the basic aqueous solution. It is.

The photosensitive resin composition for developing a basic aqueous solution according to the present invention is a photobase comprising an intramolecular cleavage reaction compound (A) that generates a basic substance by a cleavage reaction of a covalent bond in a molecule accompanying absorption of electromagnetic waves. An intramolecular solution containing a generator and a polyimide precursor or polybenzoxazole precursor soluble in a basic aqueous solution, wherein the intramolecular cleavage reaction compound (A) has a structure represented by the following formula (1 ″) It has a cleavage reaction site (a).

（式中、Ｒ１及びＲ２は、それぞれ独立に水素又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。）
上記分子内開裂反応化合物（Ａ）は、電磁波を吸収すると分子内の共有結合が切断され、各種転移反応の結果、塩基性物質を発生させるので、塩基性物質の触媒作用によって最終生成物への反応が促進されるポリイミド前駆体又はポリベンゾオキサゾール前駆体に対して、非常に有効な感光性成分として作用する。従って、本発明によれば、塩基性物質の触媒作用によって、ポリイミド前駆体又はポリベンゾオキサゾール前駆体の最終生成物への反応が促進されるために、塩基性物質と共存するポリイミド前駆体又はポリベンゾオキサゾール前駆体と、塩基性物質と共存しないポリイミド前駆体又はポリベンゾオキサゾール前駆体との間に反応温度や溶解性等に差が生じる。本発明ではこの塩基性物質の有無による差を利用して、塩基性水溶液に可溶なポリイミド前駆体又はポリベンゾオキサゾール前駆体を、塩基性物質の作用によって最終生成物への反応を促進させた状態で、例えば加熱により溶解性を低く変化させることにより、塩基性水溶液による現像が可能になる。
また、本発明において塩基性物質を発生させる当該分子内開裂反応化合物（Ａ）の分子内解裂反応部位（ａ）に含まれる化学結合は全て共有結合であるから、分子内解裂反応部位が酸と塩基とのイオン結合を有する塩の構造を含む場合とは異なり、感光性樹脂組成物中にさらに別の塩を配合する場合でもイオン交換を起こさない。それゆえ、当該分子内開裂反応化合物（Ａ）の塩基性物質を発生させる能力は、組み合わされる他の成分の影響による低下を起こしにくく、当該分子内開裂反応化合物（Ａ）を用いる感光性樹脂組成物は、処方設計の自由度が高い。
本発明の感光性樹脂組成物に用いられるポリイミド前駆体又はポリベンゾオキサゾール前駆体としては、それ自体が塩基性物質の作用によって最終生成物への反応が促進される化合物、中でも、それ自体が塩基性物質の作用によって最終生成物への反応が促進され、且つ加熱により塩基性水溶液への溶解性が低く変化する化合物が好適に用いられる。

(In the formula, R 1 and R 2 are each independently hydrogen or a monovalent organic group, and they may be the same or different. In addition, the two are bonded to form a cyclic structure. Is also good.)
When the intramolecular cleavage reaction compound (A) absorbs electromagnetic waves, the covalent bond in the molecule is cleaved, and a basic substance is generated as a result of various transfer reactions. It acts as a very effective photosensitive component for the polyimide precursor or polybenzoxazole precursor whose reaction is accelerated. Therefore, according to the present invention, since the reaction of the polyimide precursor or polybenzoxazole precursor to the final product is promoted by the catalytic action of the basic substance, the polyimide precursor or polysiloxane coexisting with the basic substance is used. A difference occurs in reaction temperature, solubility, and the like between the benzoxazole precursor and the polyimide precursor or polybenzoxazole precursor that does not coexist with the basic substance. In the present invention, a polyimide precursor or a polybenzoxazole precursor that is soluble in a basic aqueous solution is promoted to react with the final product by the action of the basic substance by utilizing the difference due to the presence or absence of the basic substance. In the state, for example, by changing the solubility low by heating, development with a basic aqueous solution becomes possible.
In the present invention, all the chemical bonds contained in the intramolecular cleavage reaction site (a) of the intramolecular cleavage reaction compound (A) that generates a basic substance are all covalent bonds. Unlike the case of including a salt structure having an ionic bond between an acid and a base, ion exchange does not occur even when another salt is added to the photosensitive resin composition. Therefore, the ability of the intramolecular cleavage reaction compound (A) to generate a basic substance is unlikely to decrease due to the influence of other components to be combined, and the photosensitive resin composition using the intramolecular cleavage reaction compound (A). Goods have a high degree of freedom in prescription design.
The polyimide precursor or polybenzoxazole precursor used in the photosensitive resin composition of the present invention is a compound that itself accelerates the reaction to the final product by the action of a basic substance, among which, itself is a base. A compound in which the reaction to the final product is promoted by the action of the active substance and the solubility in a basic aqueous solution changes with heating is preferably used.

  As one of the intramolecular cleavage reaction compounds (A), a compound (A1) represented by the following formula (1) can be used.

（式中、Ｒ１およびＲ２は、それぞれ独立に水素又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。Ｒ３およびR４は、それぞれ独立に水素又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。）

(In the formula, R 1 and R 2 are each independently hydrogen or a monovalent organic group, and they may be the same or different. In addition, they are bonded to form a cyclic structure. R3 and R4 are each independently hydrogen or a monovalent organic group, and they may be the same or different, and they may be combined to form a cyclic structure. good.)

In order to use light emitted from a high-pressure mercury lamp mainly used for patterning more efficiently, it is effective to provide absorption in a region larger than 300 nm. Thus, it is preferable that at least one of R1 or R2 of the compound (A1) represented by the formula (1) is an aromatic group from the viewpoint of achieving high sensitivity. In this case, the aromatic group means a cyclic unsaturated organic compound group, and the state in which the aromatic group is substituted for R1 or R2 means that the cyclic unsaturated organic compound is directly covalently bonded to R1 or R2. The state of being bound to the carbon to which is bound.
In this case, the cyclic unsaturated organic compound includes a heteroaromatic compound.

  In the compound (A1) represented by the formula (1), at least one of R3 and R4, the terminal atom bonded to the nitrogen atom, is a carbon atom having SP3 orbital to achieve high sensitivity. In view of the above, it is further preferable from the viewpoint of increasing the solubility contrast of the unexposed portion of the exposed portion, and it is more preferable that both R3 and R4 are so.

  In the compound (A1) represented by the above formula (1), at least one of R3 and R4 is a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. From the viewpoint of achieving high sensitivity, one or more aliphatic hydrocarbon groups selected from the group consisting of R3 and R4 are preferably 2 from the viewpoint of increasing the solubility contrast of the unexposed areas. In any case, it is even more preferable.

  In the compound (A1) represented by the above formula (1), R3 and R4 are further connected to form a cyclic structure together with nitrogen of the urethane bond structure, thereby achieving high sensitivity. Furthermore, it is preferable from the viewpoint of increasing the solubility contrast of the unexposed area of the exposed area.

  In such a case, the basicity of the basic substance generated by the irradiation of electromagnetic waves becomes stronger and the catalytic action becomes larger, so the solubility of the polymer precursor in the developer with a smaller amount of the basic substance. It becomes easy to create the difference. In other words, due to the intramolecular cleavage reaction accompanying the absorption of electromagnetic waves of the present invention, even when the sensitivity of the neutral compound itself that generates the basic substance is low, the generated basic substance has a large catalytic effect. Sensitivity is improved and a highly sensitive photosensitive resin composition can be obtained.

  Since 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, the intramolecular cleavage reaction compound (A) is 436 nm, 405 nm, 365 nm, 248 nm. It is preferable to have absorption in at least one wavelength among the electromagnetic waves having a wavelength of. Furthermore, since the polymer precursor used in the present invention often has absorption in a wavelength region of 400 nm or less, it is more preferable that the polymer precursor has absorption with respect to any wavelength of 436 nm or 405 nm.

  In one embodiment of the present invention, irradiation sensitivity can be improved by adding a sensitizer to the photosensitive 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.

Furthermore, this invention also provides the negative pattern formation method using the said photosensitive resin composition. The negative pattern forming method according to the present invention irradiates the surface of a coating film or molded body made of the photosensitive resin composition with an electromagnetic wave in a predetermined pattern, and performs post-treatment (usually heat treatment) as necessary. ) To selectively lower the solubility of the coating film or molded body in the electromagnetic wave irradiation site in the basic aqueous solution, and then developing using the basic aqueous solution.
In the negative pattern forming method, a photosensitive resin composition is formed by using the intramolecular cleavage reaction compound (A) as a photobase generator in combination with a polymer precursor soluble in a basic aqueous solution. Without using a resist film for protecting the surface of the coating film or molded body from the developer, it is possible to form a negative pattern in which development is performed with a basic aqueous solution.

As described above, according to the present invention, a photosensitive resin composition that can be developed with a basic aqueous solution by a simple technique of mixing the intramolecular cleavage reaction compound (A) with a polymer precursor. Can be prepared and used.
In addition, the photosensitive resin composition according to the present invention has various intramolecular cleavage reaction compounds (A), in particular, the compound (A1) represented by the above formula (1) functions as a photobase generator. Various polymer precursors can be used in combination, and the polymer structure finally obtained can be selected from a wide range.
Specifically, the photosensitive resin composition according to the present invention can be used in 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 utilize as an applicable photosensitive polyimide resin composition or photosensitive polybenzoxazole resin composition.

  In the present invention, since all the chemical bonds contained in the intramolecular cleavage reaction site (a) of the intramolecular cleavage reaction compound (A) that generates a basic substance are covalent bonds, the intramolecular cleavage reaction site is an acid. Unlike the case of including a salt structure having an ionic bond with a base, ion exchange does not occur even when another salt is added to the photosensitive resin composition. Therefore, the ability of the intramolecular cleavage reaction compound (A) to generate a basic substance is unlikely to decrease due to the influence of other components to be combined, and the photosensitive resin composition using the intramolecular cleavage reaction compound (A). Goods have a high degree of freedom in prescription design.

  In addition, after the surface of the coating film or molded body made of the photosensitive resin composition according to the present invention is irradiated with electromagnetic waves, the irradiated site is selectively made slightly soluble, and then the coating film made of the photosensitive resin composition. Alternatively, it is possible to form a negative pattern in which development is performed with a basic aqueous solution without using a resist film for protecting the surface of the molded body from the developer. This method has a simple patterning process, and has little adverse effect on the natural environment and occupational health.

Furthermore, since the photosensitive resin composition according to the present invention can select a polymer precursor having a wide range of structures, the polymer obtained thereby imparts functions such as heat resistance, dimensional stability, and insulation. Therefore, it is suitable as all known members and coating films 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 an element 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 and a photosensitive polybenzoxazole precursor resin composition, which are one form of the photosensitive resin composition, select a polyimide or polybenzoxazole precursor having a wide range of structures. Therefore, the cured product obtained thereby can impart the functions that polyimide and polybenzoxazole have characteristically such as heat resistance, dimensional stability, insulation, etc. It is suitable as a film, a coating film or a three-dimensional structure for all known members applied.

The present invention will be described in detail below.
In the present invention, the electromagnetic wave that induces intramolecular cleavage is not limited as long as it can cause an intramolecular cleavage reaction of a compound, and includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also electron beams. Such particle beam, and radiation or ionizing radiation which collectively refers to electromagnetic wave and particle beam are included.

  The photosensitive resin composition for developing a basic aqueous solution according to the present invention (hereinafter simply referred to as a photosensitive resin composition) is an intramolecular cleavage reaction compound that generates a basic substance by a covalent bond cleavage reaction accompanying absorption of electromagnetic waves. It contains (A) and a polymer precursor that is soluble in a basic aqueous solution. Here, the basic substance generally refers to an organic compound having a pH greater than 7, and specific examples include primary and / or secondary and / or tertiary amino compounds. .

The present inventor has previously found that polyamic acid can lower the temperature at which the imidization reaction is initiated by the catalytic action of a basic substance, and can be used for patterning that enables basic aqueous development. A method has been proposed (Japanese Patent Application No. 2005-105443 that has not been published at the time of this application).
On the other hand, oxime ester compounds have been reported to undergo an intramolecular cleavage reaction by absorption of electromagnetic waves according to the following reaction formula to generate amines (Journal of Photopolymer Science and Technology Vol.15 2002 145-152).

The inventor paid attention to the intramolecular cleavage reaction of the oxime ester compound and advanced the research, and obtained the following knowledge.
The oxime ester compound is a neutral compound, but exhibits basicity when it undergoes intramolecular cleavage by absorbing electromagnetic waves and produces amine or hydrazine. 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 oxime ester compound, and by converting from neutral to basic 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 an oxime ester compound and a polyimide precursor, imidization proceeds in a place where an amine exists after irradiating an electromagnetic wave to a 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, so that the solubility is lowered. be able to. Then, according to the objective, it can heat-harden further and can be set as a polyimide pattern.

  Furthermore, the oxime ester compound can shift the absorption wavelength to the long wavelength side by introducing an aromatic ring as a substituent, and high sensitivity can be expected in combination with a polymer precursor having high permeability.

As a compound that generates an amine with the absorption of electromagnetic waves, there is a salt composed of a carboxylic acid and an amine. Certain salts of carboxylic acids and amines decompose to generate amines by photodecarboxylation. However, when the intramolecular cleavage reaction site of the photobase generator contains a salt structure having an ionic bond, if another salt is added to the photosensitive resin composition, ion exchange occurs and a photobase is generated. There is a risk that the ability to be reduced.
On the other hand, when all the chemical bonds contained in the intramolecular cleavage reaction site of the photobase generator are covalent bonds, such as oxime ester compounds, the ability to generate a basic substance is Less prone to degradation due to the effects of ingredients. Therefore, the photosensitive resin composition has a high degree of freedom in formulation design.
Furthermore, since the oxime ester compound can be easily synthesized by the reaction of the oxime compound and the carboxylic acid chloride or the reaction of the oxime compound and the isocyanate compound, the cost can be reduced.

Based on the above findings, the inventors have used, as a photobase generator, an intramolecular cleavage reaction compound (A) having an intramolecular cleavage reaction site (a) composed of only covalently bonded atoms. By using the intramolecular cleavage reaction compound (A), an amine is generated along with the absorption of electromagnetic waves, and the exposed portion is cured by imidizing the polyimide precursor using the generated amine as a catalyst. It has been found that a difference in solubility in a developing solution, particularly a basic aqueous solution, can be imparted between a portion and an unexposed portion.
This intramolecular cleavage reaction compound (A) not only promotes imidation of a polyimide precursor, but also a polymer precursor that catalyzes a reaction in which a base is converted into a final product, like a polyimide precursor. Or it acts as a very effective photosensitive component for a composition containing a system in which a target reaction proceeds by the action of a base.

  In the present invention, a photosensitive resin composition can be prepared at a low cost by a simple method of simply mixing an intramolecular cleavage reaction compound (A) with a polymer precursor. 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 the field where the characteristics of the photosensitive polyimide precursor resin composition, the photosensitive polybenzoxazole precursor resin composition, and the cyclized products thereof, which are typical examples thereof, can be utilized.

  In the present invention, as the intramolecular cleavage reaction compound (A), a compound having an intramolecular cleavage reaction site (a) composed only of atoms bonded by a covalent bond is used. Such an intramolecular cleavage reaction site (a) includes a structure represented by the following formula (1 ′) (structure having an oxime ester skeleton) or a structure represented by the following formula (1 ″). The thing containing (structure which has oxime urethane frame | skeleton) can be illustrated.

（式中、Ｒ１及びＲ２は、それぞれ独立に水素原子又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。）

(In the formula, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different. In addition, the two are bonded to form a cyclic structure. May be.)

（式中、Ｒ１及びＲ２は、それぞれ独立に水素原子又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。）

(In the formula, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different. In addition, the two are bonded to form a cyclic structure. May be.)

  Above all, the generation of the basic substance by the reaction of (IIb) in Scheme II is generated more efficiently than the generation of the basic substance by the reaction of (Ia) in Scheme I and (IIa) in Scheme II. In order to further improve the sensitivity, the structure represented by the following formula (1 ″) (structure having an oxime urethane skeleton) is subjected to an intramolecular cleavage reaction so that a basic substance can be generated by the reaction of (IIb). What is contained as a part (a) is more preferable.

  As a preferable example of the intramolecular cleavage reaction compound (A), an oxime ester compound (A1) having an oxime urethane skeleton represented by the following formula (1) can be used.

（式中、Ｒ１及びＲ２は、それぞれ独立に水素原子又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。Ｒ３およびR４は、それぞれ独立に水素原子又は１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していても良い。）

(In the formula, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different. In addition, the two are bonded to form a cyclic structure. R3 and R4 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different, and the two are bonded to form a cyclic structure. May be.)

In addition to a hydrogen atom, a monovalent organic group may be introduced at the positions of R1 and R2 in formula (1 ′), formula (1 ″) and formula (1). R1 and R2 are the same as each other. R3 and R4 may be bonded to each other to form a cyclic structure.
Examples of other monovalent organic groups that can be introduced at the positions of R1 and R2 include groups having a hydrocarbon skeleton, and they may contain bonds other than hydrocarbons such as heteroatoms and substituents. Such a heteroatom portion may be incorporated into an aromatic ring to form a heterocyclic ring. Examples of the group having a hydrocarbon skeleton include, for example, a linear or branched saturated or unsaturated hydrocarbon group, a linear or branched saturated or unsaturated alkyl ether group, an aryl ether group, a linear or branched saturated Or an unsaturated alkyl thioether group, an aryl thioether group, a linear or branched saturated or unsaturated halogenated alkyl group, or an aromatic group such as phenyl or naphthyl, or a linear or branched saturated or unsaturated group Contains a hetero atom or hetero atom such as halogen atom, hydroxyl group, mercapto group, cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group on the hydrocarbon skeleton of Examples include various groups formed by bonding groups.
In addition, R1 and R2 in Formula (1 ′), Formula (1 ″), and Formula (1) preferably have about 1 to 25 carbon atoms.

  In addition, the wavelength of light to be absorbed is adjusted by changing the structure of the substituent introduced into any one of R1 and R2 in formula (1 ′), formula (1 ″) and formula (1). It is possible to absorb a desired wavelength by introducing an optimum substituent according to the wavelength to be absorbed.

In particular, R1 and R2 can be introduced by selecting the type of substituent relatively freely from the viewpoint of adjusting the absorption wavelength. By appropriately selecting R1 and R2, it is possible to efficiently absorb electromagnetic waves, easily cause intramolecular cleavage, and achieve high sensitivity.
Among these, from the viewpoint of being able to absorb electromagnetic waves on the long wavelength side, a structure having π electrons is preferable, and specific examples include aromatic groups and vinyl groups. These substituents may further have a substituent. The longer the π-electron contained in the substituent is conjugated, the longer the wavelength is absorbed, and the structure can be appropriately selected depending on the exposure wavelength.
When the light source at the time of exposure is a high-pressure mercury lamp, from the viewpoint of absorption wavelength and heat resistance, more specifically, in order to have absorption in a region larger than 300 nm, at least one of substituents R1 and R2. One is preferably an aromatic group.
The aromatic group in this case means a cyclic unsaturated organic compound group, and the state in which the aromatic group is substituted for R1 or R2 means that the cyclic unsaturated organic compound is directly covalently bonded to R1 or R2. The state of being bound to the carbon to which is bound. In this case, the cyclic unsaturated organic compound includes a heteroaromatic compound containing a hetero atom.

Specific examples of the cyclic unsaturated organic compound group include a substituted or unsubstituted phenyl group, biphenyl group, terphenyl group, naphthyl group, anthranyl group, phenanthrenyl group, pyrenyl group, and other aromatic hydrocarbon groups, as well as furanyl. And heteroaromatic compounds such as a group, a thiophenyl group, a pyrrolyl group, a (thio) xanthenyl group, a (thio) xanthonyl group, a coumaryl group, and an anthraquinolyl group.
Substituents may be introduced into this cyclic unsaturated organic compound group, specifically, halogen atoms, hydroxyl groups, mercapto groups, cyano groups, silyl groups, silanol groups, alkoxy groups, nitro groups, carboxyl groups, acetyl groups. Group, acetoxy group, sulfone group, unsaturated alkyl ether group, aryl ether group, unsaturated alkyl thioether group, aryl thioether group and the like are not particularly limited. Among them, an alkoxy group, an amide group, Introduction of a dimethylamino group or the like is effective from the viewpoint of increasing the absorption wavelength, but it is necessary to select the oxime ester compound (A1) into which the substituent is introduced in consideration of the pH. From these viewpoints, the alkoxy group is the most effective.

Interpretation of the Ultraviolet Spectra of Natural Products (AIScott 1964) and identification methods based on the spectrum of organic compounds as a guideline on what substituents should be introduced to shift the absorption wavelength with respect to the desired wavelength 5th edition (RMS
ilverstein 1993) can be referred to.

  These substituents may be introduced at any stage in the synthesis, and may be introduced after an oxime ester compound, or may be synthesized using the originally introduced raw material as a starting material, or an intermediate. It may be introduced in this state, and is not particularly limited.

  In addition to the hydrogen atom, a monovalent organic group may be introduced at the positions of R3 and R4 in the oxime ester compound (A1) represented by the above formula (1) represented by the formula (1). R3 and R4 may be the same as or different from each other. R3 and R4 may be bonded to each other to form a cyclic structure.

Examples of monovalent organic groups that can be introduced at the positions of R3 and R4 include, in addition to hydrogen atoms, linear or branched saturated or unsaturated hydrocarbon groups, or aromatic groups such as phenyl and naphthyl, or these A linear or branched saturated or unsaturated hydrocarbon group having an aromatic group such as benzyl or phenethyl as a substituent, or a linear or branched saturated or unsaturated hydrocarbon group such as tolyl or cumenyl. Examples thereof include an aromatic group as a substituent, and a cyclic saturated hydrocarbon group. The unsaturated hydrocarbon includes a carbon-carbon triple bond as well as a carbon-carbon double bond.
The monovalent organic group that can be introduced at the position of R3 or R4 includes a bond other than a hydrocarbon such as a heteroatom or a substituent in the hydrocarbon chain of the hydrocarbon group mentioned above. It may be a group having such a hydrocarbon skeleton. In addition, the monovalent organic group that can be introduced at the positions of R3 and R4 particularly has about 1 to 20 carbon atoms, and preferably about 1 to 8 carbon atoms. These may be linear, branched or cyclic. R4 and R8 may be connected to form a ring.
Non-hydrocarbon bonds such as heteroatoms contained in a group having a hydrocarbon skeleton include ether bond, thioether bond, carbonyl bond, ester bond, thioester bond, amide bond, urethane bond, carbonate bond, acyl bond, and oxime bond. As substituents, halogen atoms, hydroxyl groups, mercapto groups, cyano groups, silyl groups, silanol groups, alkoxy groups, nitro groups, carboxyl groups, acetyl groups, acetoxy groups, sulfone groups, unsaturated alkyl ether groups, aryl An ether group, an unsaturated alkyl thioether group, an aryl thioether group and the like can be mentioned, but are not particularly limited.

The thermal properties and basicity of amines and hydrazines generated from oxime ester compounds differ depending on the substituents introduced at the positions of R3 and R4. The amine or hydrazine having higher basicity has a stronger catalytic action for a dehydration condensation reaction such as imidization, and a dehydration condensation reaction at a lower temperature is possible with a smaller amount of addition. That is, even when the sensitivity of the oxime ester compound (A1) itself to the electromagnetic wave is low, the apparent sensitivity is improved because the generated basic substance has a large catalytic effect.
In view of the large catalytic effect as described above, the basic substance generated by the cleavage reaction accompanying the absorption of electromagnetic waves of the oxime ester compound (A1) is preferably an aliphatic amine or an aliphatic hydrazine. Among these, secondary aliphatic amines are preferable from the viewpoint of basicity, and primary aliphatic amines are preferable from the viewpoint of ease of synthesis of the oxime ester compound. As a result of the examination so far, the difference in the catalytic action between the primary amine and the secondary amine is small in the aliphatic amine, so the oxime ester compound that generates the primary aliphatic amine that is easy to synthesize is more suitable. More practical.

From the viewpoint of generating such an aliphatic amine, achieving high sensitivity, and increasing the solubility contrast of the unexposed area of the exposed area, R3 of the compound (A1) represented by the above formula (1) and It is preferable that at least one terminal atom bonded to a nitrogen atom in R4 is a carbon atom having an SP3 orbital. Especially, it is preferable that the terminal atom couple | bonded with the nitrogen atom is a carbon atom which has SP3 orbital in both R3 and R4.
Specific examples of the substituent in which the terminal atom bonded to the nitrogen atom is a carbon atom having SP3 orbital include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, n- Examples include, but are not limited to, a butyl group, a cyclohexyl group, an isobornyl group, a norbornyl group, an adamantyl group, and a benzyl group.
Further, at least one of R3 and R4 of the compound (A1) represented by the formula (1) is composed of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. It is preferably one or more aliphatic hydrocarbon groups selected from the group. In particular, both R3 and R4 are one or more aliphatic hydrocarbon groups selected from the group consisting of linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups. Preferably there is. The suitably used aliphatic hydrocarbon group may have a substituent such as an aromatic group, or may contain a bond other than hydrocarbon such as a heteroatom in the hydrocarbon chain. good. R3 and R4 may be connected to each other.

  On the other hand, the intramolecular cleavage reaction compound has a lower number of moles when considered at the same weight with a low molecular weight. The catalytic effect of a basic substance generated by absorption of electromagnetic waves is proportional to the number of molecules of the basic substance. Therefore, when the sensitivity to electromagnetic waves is the same, a lower molecular weight intramolecular cleavage reaction compound is used in a smaller amount. It is possible to generate a basic substance capable of exhibiting a sufficient catalytic effect with the addition of. That is, from this point, when R3 and R4 of the compound (A1) represented by the above formula (1) are linked to form a hydrocarbon group that forms a cyclic structure with nitrogen of the urethane bond structure, the oxime urethane compound is This is preferable because the molecular weight can be reduced. Furthermore, the generated amine becomes a secondary amine, and since the molecular size is small and it is easy to diffuse, the sensitivity is also improved. Specific examples of R3 and R4 include, but are not limited to, the following structures.

  In addition, as the intramolecular cleavage reaction compound (A) of the present invention, a compound containing a structure (structure having an oxime ester skeleton) represented by the following formula (1 ′) in two or more positions in the molecule, or the following formula A compound containing a structure represented by (1 ″) (a structure having an oxime urethane skeleton) may be used. For example, a compound that generates a diamino compound by intramolecular cleavage such as the following formula (2) Examples thereof include compounds in which two urethane bonds are bonded to a skeleton having two oxime-derived sites such as the following formulas (3) and (4), but are not particularly limited.

(In Formula (2), R5, R6, R7 and R8 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different. And X may be a divalent amine residue.
(In the formula (3), R9 and R10 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different. R11, R12, R13, and R14 each independently represent a hydrogen atom or a monovalent organic group, and they may be the same or different, and the two are (It may be bonded to form a cyclic structure. Y is a divalent organic group.)
(In the formula (4), R9 and R10 are each independently a hydrogen atom or a monovalent organic group, and they may be the same or different. (Y may be a divalent organic group.)

  In the above formula (2), R5, R6, R7 and R8 may be the same as R1 and R2 in the formula (1), respectively. X is a divalent amine residue, for example, piperazine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-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'-diamino Phenylmethane, 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- 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-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- Ditrifluoromethylbenzyl) 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] Heptane, a diamine obtained by substituting some or all of the hydrogen atoms on the aromatic ring of the diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group However, the present invention is not limited thereto.

In the formulas (3) and (4), R9 and R10 may be the same as R1 and R2 in the formula (1), respectively. Moreover, R11, R12, R13, and R14 in Formula (3) can use the same thing as R3 and R4 of Formula (1), respectively.
Y is a divalent organic group, which is a divalent saturated or unsaturated alkylene group such as an ethylene group, an arylene group such as a phenylene group or a naphthylene group, or a combination of the alkylene group and the arylene group. And those having a substituent bonded thereto. Further, they may have a hetero atom, such as an ether bond, an ester bond, an amide bond or the like in the main chain.

  Examples of the intramolecular cleavage reaction compound (A) used in the present invention include the following compounds, but are not limited thereto.

  Examples of basic substances generated by intramolecular cleavage of the intramolecular cleavage reaction compound (A) used in the present invention include primary amines such as n-butylamine, benzylamine, amylamine, hexylamine and octylamine, Secondary amines such as diethylamine, dipropylamine, diisopropylamine and dibutylamine, alkylenediamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine, and triamines such as diethylenetriamine Other amines such as tetramine compounds and benzylamine are exemplified, but are not particularly limited as long as the conditions disclosed in the present invention are applicable.

In addition, the intramolecular cleavage reaction compound (A) such as the oxime ester compound (A1) preferably does not decompose at the temperature of heating performed when the coating film of the photosensitive resin composition of the present invention is dried. Furthermore, it is preferable not to decompose during the heating after the exposure and before the development (operation for selectively accelerating imidization of the exposed portion by the action of the basic substance generated by the exposure). Specifically, the temperature when the intramolecular cleavage reaction compound (A) such as the oxime ester compound (A1) is heated to reduce 5% weight from the initial weight (5% weight reduction temperature) is 100 ° C. The above is preferable.
In addition, 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, it is generated by absorption of an intramolecular cleavage reaction compound (A) and electromagnetic waves. The decomposed product is preferably decomposed or volatilized by a heating process performed after development (for example, when the polymer is a polyimide precursor, an imidization process). Specifically, when the intramolecular cleavage reaction compound (A) such as the oxime ester compound (A1) or the decomposition product generated by the absorption of electromagnetic waves is heated to reduce the weight by 50% from the initial weight. The temperature (50% weight loss temperature) is preferably 400 ° C. or lower.

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.
Furthermore, the polymer precursor used in the present invention is soluble in a basic aqueous solution and is soluble in the basic aqueous solution. Specifically, the polymer precursor 25 of the coating film formed on the substrate is used. The dissolution rate with respect to a 0.1 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 100 ° C. is 100 kg / sec or more. The dissolution rate is more preferably 1000 kg / sec or more. Furthermore, the dissolution rate with respect to a 2.38 wt% tetramethylammonium hydroxide aqueous solution, which is a more commonly used developer, is preferably 100 kg / sec or more, and more preferably 1000 kg / sec or more. . When the dissolution rate according to the above definition is less than 100 Å / sec, the development time is delayed, workability and productivity are deteriorated, and it is difficult to obtain a solubility contrast between the exposed and unexposed areas.
Accordingly, the dissolution rate of the photosensitive resin composition of the present invention in a basic aqueous solution is 100 Å / sec or more at 25 ° C. in a 0.1 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. It is preferable that it is 1000 liters / sec or more. Furthermore, the dissolution rate with respect to a 2.38 wt% tetramethylammonium hydroxide aqueous solution, which is a more commonly used developer, is preferably 100 kg / sec or more, and more preferably 1000 kg / sec or more. .

  As a specific procedure for measuring the dissolution rate, a polymer precursor coating film formed on a substrate such as an alkali-free glass was heated to 25 ° C. and stirred with a developer (in this case, 0.1%). The difference between the initial film thickness and the film thickness measured after being immersed in a weight% TMAH aqueous solution or 2.38 wt% TMAH aqueous solution for a certain period of time, rinsed with distilled water and dried The amount of film reduction divided by the time immersed in the developer is the dissolution rate per unit time at 25 ° C.

In addition, when a photosensitive resin composition is actually used in a predetermined photosensitive pattern formation process in order to obtain sufficient solubility contrast between the exposed area and the unexposed area, pattern exposure and, if necessary, The ratio of the solubility of the unexposed part and the exposed part in the developing solution before the developing process, obtained by performing a post-process (usually a heating process) (dissolution rate per unit time in the developing solution of the unexposed part / exposed part) The dissolution rate per unit time in the developer is preferably 10 or more.
The dissolution rate per unit time is determined in the same manner as in the above method. After the pattern exposure is performed on the coating film of the photosensitive resin composition and the heating after the exposure is performed, the dissolution rate of the exposed area and the unexposed area is determined. For each.

In the present invention, a polymer precursor whose reaction to the final product is promoted by the action of a basic substance is typically used. Here, the mode in which the reaction of the polymer precursor to the final product is promoted by the action of the basic substance is only the mode in which the polymer precursor is changed to the final product only by the action of the basic substance. In addition, an embodiment is included in which the reaction temperature of the polymer precursor to the final product is lowered by the action of the basic substance as compared with the case where there is no action of the basic substance.
If there is a reaction temperature difference due to the presence or absence of such a basic substance, an appropriate temperature at which only the polymer precursor coexisting with the basic substance reacts to the final product using the reaction temperature difference. By heating at, only the polymer precursor coexisting with the basic substance reacts with the final product, and the solubility in the basic aqueous solution changes. Accordingly, the solubility of the polymer precursor in the basic aqueous solution can be changed depending on the presence or absence of the basic substance, and thus patterning by the basic aqueous solution development becomes possible. Therefore, as a polymer precursor used in the present invention, the reaction to the final product is promoted by the action of a basic substance, and the solubility in a basic aqueous solution is lowered by heating compared to before heating. A polymer precursor is preferably used.

As the polymer precursor in the present invention, a polyimide precursor or a polybenzoxazole precursor is particularly preferably used. As the polyimide precursor and polybenzoxazole precursor, any polyimide precursor or polybenzoxazole precursor can be used because of its mechanism, and a mixture of two or more separately synthesized polymer precursors. But it ’s okay.
Here, polyamic acid is preferably used as the polyimide precursor soluble in the basic aqueous solution, and polyamide alcohol is preferably used as the polybenzoxazole precursor.
Since polyamic acid can be obtained only by mixing acid dianhydride and diamine in a solution, it can be synthesized by a one-step reaction, is easy to synthesize and can be obtained at low cost, and is preferable.

  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 an intramolecular cleavage reaction are used. An electromagnetic wave is irradiated to the part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the compound (A). Then, a basic substance 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 a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired two-dimensional resin pattern (general plane pattern) or three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

In the present invention, the intramolecular cleavage reaction compound (A) functions as a highly sensitive photobase generator, and between the electromagnetic wave irradiation site and the non-irradiation site on the coating film or molded body of the photosensitive resin composition. Therefore, excellent developability can be obtained even when a basic aqueous solution is used instead of an organic solvent.
As a secondary effect, when the polymer precursor to be used is a polyamic acid, it is sufficient even if the temperature required for imidization is low due to the catalytic effect of the basic substance. It can be lowered to 250 ° C. or lower. In order to imidize the conventional polyamic acid, the final cure temperature had to be 300 ° C. or higher, so the use was limited. However, it became possible to lower the final cure temperature, so a wider range Applicable to usage.

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

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

  Examples of the acid dianhydride applicable to the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic dianhydride. , Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarbo) Ciphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoro Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4- Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) Phenoxy] phenyl} propa Dianhydride,

2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, 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 an acid dianhydride into which fluorine is introduced or an acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the transparency of the polyimide precursor is improved. Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. When used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small.

  On the other hand, the amine component can also be used alone or in combination of two or more diamines. The diamine component used is not limited, but p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -Diaminodiph Nylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2 -Di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1 -Phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis ( 3-Aminophenoxy) benzene, 1,3 Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis ( 4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dito Trifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2 , 6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-amino) Phenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzen) ) Phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4 , 4′-Dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) -3,3 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, , 3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis ( -Aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis ( 2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether,

1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2 -Aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, 11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohex 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2- Aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2. 1] A diamine obtained by substituting some or all of the hydrogen atoms on the aromatic ring of the above diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group. Can be used.
Furthermore, depending on the purpose, any one or two or more of the ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate group, and isopropenyl group serving as a crosslinking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient. Rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like can be mentioned.
In addition, diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring, for example, There exists what is represented by following formula (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 technique which synthesize | combines the oxime ester compound (A1) and polyimide precursor which are used by this invention is illustrated more concretely from this, this invention is not limited to this.
The oxime ester compound (A1) of the present invention can be obtained, for example, by the one-step reaction scheme described below. According to this reaction scheme, acetophenone oxime is used as a starting material, and this is reacted with phenylacetic chloride in the presence of a triethylemine catalyst to obtain the desired product.
Further, as another technique, there is exemplified a technique in which acetophenone oxime is used as a starting material and this is reacted with phenyl isocyanate in the presence of a dibutyltin diacetate catalyst to obtain a target product.
However, the synthesis route is not limited to this as long as the structure according to the present invention is finally obtained.

The oxime ester compound (A1) of the present invention thus obtained needs to have an 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 oxime ester compound (A1) and the other intramolecular cleavage reaction compound (A) have absorption with respect to electromagnetic waves having at least one wavelength among electromagnetic waves having wavelengths of at least 436 nm, 405 nm, 365 nm, and 248 nm. It is preferable that
In particular, when the polymer precursor used in the present invention is a polymer containing an aromatic component, the UV absorption of the polymer precursor often exists up to a long wavelength region. Therefore, the oxime ester compound (A1) The absorption wavelength is more preferably present in a wavelength region where the polymer precursor sufficiently transmits light, specifically in 436 nm and 405 nm.
In this case, having absorption means that the molar extinction coefficient at each wavelength in a state dissolved in a solution such as acetonitrile may be 300 or more, and more preferably 500 or more.

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 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, the polyimide precursor has a film thickness of 1 μm and at least 5 for any of the exposure wavelengths. % Or more is preferable, and it is more preferable that the transmittance is 15% or more.
That the transmittance | permeability of a polyimide precursor is high with respect to exposure wavelength means that there is little loss of irradiation 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 is a molecular weight obtained by a known method, and is exemplified by a value in terms of polystyrene by gel permeation chromatography (GPC). In this case, the molecular weight of the polyimide precursor itself may be used, or the molecular weight after chemical imidization treatment with acetic anhydride or the like may be used.

  The photosensitive resin composition according to the present invention may be a simple mixture of only an intramolecular cleavage reaction compound (A), a polyimide precursor, and a solvent, but further suitably a sensitizer, light or thermosetting. The photosensitive resin composition may be prepared by blending other components such as a non-polymerizable binder resin other than the photosensitive component and the polyimide precursor. In the intramolecular cleavage reaction compound (A) used in the present invention, since the intramolecular cleavage site does not contain a salt structure, it is difficult for the base generation ability to be lowered by other components blended in the photosensitive resin composition. High degree of freedom in prescription design.

Addition of a sensitizer may be effective when it is desired to improve the sensitivity by allowing the oxime ester compound (A1) to sufficiently absorb electromagnetic waves having a wavelength that passes through the polymer precursor.
In particular, when the absorption of the polymer precursor is also at a wavelength of 360 nm or longer, the effect of adding a sensitizer is great. Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, cyanine and derivatives thereof, merocyanine and derivatives thereof, coumarins and derivatives thereof, ketocoumarins and derivatives thereof, and ketobiscoumarins. And derivatives thereof, cyclopentanone and derivatives thereof, cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, quinoline derivatives and derivatives thereof, styrylquinoline derivatives and derivatives thereof, thioxanthene derivatives, xanthene derivatives and Derivatives, oxonol-based and derivatives thereof, rhodamine-based and derivatives thereof, pyrylium salts and derivatives thereof.

Specific examples of cyanine, merocyanine and derivatives thereof include 3,3′-dicarboxyethyl-2,2′thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide, 1,3′-diethyl-2,2′-quinothiocyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolidene) ethylidene] -2-thioxo-4- And oxazolidine.
Specific examples of coumarin, ketocoumarin and derivatives thereof include 3- (2′-benzimidazole) -7-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylaminocoumarin), and 3,3′-carbonylbiscoumarin. 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin) and the like.
Specific examples of thioxanthone and derivatives thereof include diethyl thioxanthone and isopropyl thioxanthone.

In addition, benzophenone, acetophenone, anthrone, p, p'-tetramethyldiaminobenzophenone (Michler ketone), phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-acetyl-p-nitroaniline, p-nitro Aniline, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, N-acetyl-4-nitro-1-naphthylamine, picramide, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9- Benzanthrone, p, p'-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, 1,2-naphthoquinone, 2,5-bis- (4'-diethylaminobenzal) -cyclopentane, 2,6-bis- (4′-diethyla Minobenzal) -cyclohexanone, 2,6-bis- (4′-dimethylaminobenzal) -4-methyl-cyclohexanone, 2,6-bis- (4′-diethylaminobenzal) -4-methyl-cyclohexanone, 4, 4'-bis- (dimethylamino) -chalcone, 4,4'-bis- (diethylamino) -chalcone, p-dimethylaminobenzylideneindanone, 1,3-bis- (4'-dimethylaminobenzal) -acetone 1,3-bis- (4′-diethylaminobenzal) -acetone, N-phenyl-diethanolamine, Np-tolyl-diethylamine, and the like.
Since these exhibit particularly excellent effects when combined with the oxime ester compound (A1), a sensitizer exhibiting an optimal sensitizing action is appropriately selected depending on the structure of the oxime ester compound (A1). In this case, it is preferable that the sensitizer is not basic, that is, a compound having a pH of 7 or less.

  Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition. Moreover, when using a 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.

Moreover, you may add to the photosensitive resin composition of this invention the other photosensitive component which generate | occur | produces an acid or a base with light as an auxiliary | assistant role of the intramolecular cleavage reaction compound (A).
In addition, various organic or inorganic low-molecular or high-molecular compounds may be blended to impart processing characteristics and various functionalities to the resin composition according to the present invention. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

In the photosensitive resin composition according to the present invention, the polymer precursor (solid content) is based on the entire solid content of the photosensitive resin composition from the viewpoint of film physical properties of the pattern to be obtained, particularly film strength and heat resistance. 30% by weight or more, preferably 50% by weight or more. The intramolecular cleavage reaction compound (A) is usually 0.1 to 95 parts by weight, preferably 0.5 to 100 parts by weight of the solid content of the polymer precursor contained in the photosensitive resin composition. It is preferable to make it contain in the range of -60 weight part, More preferably in the range of 1-40 weight part. If the amount is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and if it exceeds 95 parts by weight, it is 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.

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

The glass transition temperature of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance, but in applications where a thermoforming process is considered like an optical waveguide, It is preferable to show a glass transition temperature of about 120 ° C. to 450 ° C., and it is more preferable to show a glass transition temperature of about 200 ° C. to 400 ° 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 apparatus 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, the photosensitive resin composition according to the present invention has an intramolecular cleavage reaction compound (A), particularly an oxime ester compound (A1) represented by the above formula (1). By functioning as a base generator, a wide variety of polymer precursors can be applied, and the polymer structure finally obtained can be selected from a wide range.
Moreover, according to this invention, since the photosensitive resin composition can be obtained by the simple method of mixing only the intramolecular cleavage reaction compound (A) with a polymer precursor, it is excellent also in cost performance.
Furthermore, since the treatment temperature required for imidization can be reduced by the catalytic effect of the amine generated by the irradiation of electromagnetic waves, it is possible to reduce the impossibility of the process and damage to the product due to heat.

  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.

Next, the negative pattern forming method according to the present invention irradiates the surface of the coating film or the molded body made of the photosensitive resin composition for basic aqueous solution development according to the present invention with an electromagnetic wave in a predetermined pattern, A post-treatment is performed as necessary to selectively reduce the solubility of the coating film or molded body in the electromagnetic wave irradiation site in the basic aqueous solution, and then development is performed using the basic aqueous solution.
When the photosensitive resin composition according to the present invention is applied on some support and irradiated with electromagnetic waves in a predetermined pattern, the intramolecular cleavage reaction compound (A) is cleaved only in the exposed area, and thus a basic substance. Produces. The basic substance acts as a catalyst that promotes the reaction of the polymer precursor in the exposed area to the final product.

When the basic substance reacts directly with the polymer precursor in the exposed area to the final product and the solubility of the exposed polymer precursor only in the basic aqueous solution is selectively reduced, It becomes possible to develop by dissolving only the unexposed part where the solubility is not lowered after the exposure using a basic aqueous solution without any post-treatment.
The exposure method and exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure, and any known means such as a stepper, scanner, aligner, contact printer, laser, and electron beam drawing can be used. .

In the negative pattern forming method according to the present invention, post-treatment such as heat treatment may be performed between the exposure step and the development step as necessary. The post-treatment here is a treatment for selectively reducing the solubility of the coating film or the molded body in the basic aqueous solution at the electromagnetic wave irradiation site.
The post-treatment such as heat treatment is, for example, a treatment in which only the polymer precursor in the exposed portion coexisting with the basic substance is reacted with the final product. Therefore, when performing the heat treatment, for example, it is performed at a temperature at which the cyclization rate of the polymer precursor is different between the exposed portion where the basic substance is present and the unexposed portion where the basic substance is not present. Is preferred.

For example, when imidating a polyimide precursor, the preferable temperature range of the heat treatment at this stage 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, a neutral compound that generates a basic substance is thermally decomposed by an intramolecular cleavage reaction accompanying absorption of electromagnetic waves, or even in an unexposed area where no amine is present. Due to the progress of imidization, a difference in solubility between the exposed portion and the unexposed portion is difficult to occur.
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 basic aqueous solution used in the development step is not particularly limited. For example, a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 0.01 wt% to 10 wt%, preferably 0.05 wt% to 5 wt%, Potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, sodium hydrogen carbonate aqueous solution, other primary, secondary and tertiary amine aqueous solutions, hydroxide ion and ammonium ion salt aqueous solutions Etc.
The solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.

(Production Example 1)
Under a nitrogen atmosphere, 1.35 g (10 mmol) of acetophenone oxime was dissolved in 50 mL of dehydrated dimethylacetamide in a 200 mL three-necked flask, and a catalytic amount of dibutyltin diacetate was added and stirred. Thereto was added 1.33 g (10 mmol) of benzyl isocyanate, and the mixture was heated and stirred at 105 ° C. for 7 hours.
Thereafter, reprecipitation was performed with 500 ml of distilled water, and the precipitate was collected and then produced by column chromatography to obtain 1.6 g of the intended photosensitive material 1.

(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 80 mg of the photosensitive substance 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 of a comparative example (comparative photosensitive resin composition 1).

(Test)
(1) Absorption wavelength and transmittance The UV absorption of the photosensitive material 1 in a 1.0 × 10 ⁻⁴ mol / L acetonitrile solution and the transmittance of 4.11 μm created on the glass of the polyimide precursor 1 were spectroscopically analyzed. It measured using the measuring apparatus (UV-2550 (PC) S GLP by SHIMADZU).
As a result, in the UV absorption spectrum of photosensitive material 1, the bottom of the absorption extended to around 350 nm. Moreover, the transmission spectrum of the polyimide precursor 1 is shown in FIG.
The transmittance of the polyimide precursor was as shown in Table 1, and showed a transmittance of 10% or more even at 365 nm.

(2) Thermosetting temperature Spin the photosensitive resin composition 1 (Example 1) and the comparative photosensitive resin composition 1 (Comparative Example 1) on a chrome-plated glass plate to a final film thickness of 2 μm. Coated and dried on a hot plate at 100 ° C. for 2 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 IR310 manufactured by JASCO Corporation and HOTPLATE EC-1200 manufactured by ASONE Co., Ltd. while heating from room temperature to 350 ° C. at a heating rate of 5 ° C./min.
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 set to 1, the amount of decrease in the peak area in the heating process was converted into the imidation rate and plotted. (The state before measurement was 0% imidation, and the time when the peak completely disappeared was taken as 100% imidation.)
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.

(3) 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. Then, 5J ultraviolet irradiation was performed on a hot plate at 160 ° C. using a manual exposure apparatus (MA-1200, manufactured by Dainippon Screen Co., Ltd.), through a photomask having a predetermined pattern. After heating for a minute, it was immersed in a tetramethylammonium hydroxide 2.38% solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 300 ° 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.

It is a graph which shows the transmission spectrum of the polyimide precursor used in the Example. It is a graph which shows the relationship between the processing temperature after irradiating the photosensitive resin composition of an Example and a comparative example with an ultraviolet-ray, and the imidation ratio of a polyimide precursor.

Claims (17)

A photobase generator composed of an intramolecular cleavage reaction compound (A) that generates a basic substance by the cleavage reaction of a covalent bond in the molecule accompanying absorption of electromagnetic waves, and a polyimide precursor or polysoluble in a basic aqueous solution. A benzoxazole precursor is contained, and the intramolecular cleavage reaction compound (A) has an intramolecular cleavage reaction site (a) including a structure represented by the following formula (1 ″). Photosensitive resin composition for basic aqueous solution development.

(In the formula, R 1 and R 2 are each independently hydrogen or a monovalent organic group, and they may be the same or different. In addition, the two are bonded to form a cyclic structure. Is also good.) The photosensitive resin composition for basic aqueous solution development according to claim 1, wherein the polyimide precursor or the polybenzoxazole precursor itself is a substance whose reaction to the final product is promoted by the action of a basic substance. object. The polyimide precursor or the polybenzoxazole precursor itself is a substance whose reaction to the final product is promoted by the action of a basic substance, and its solubility in a basic aqueous solution is lowered by heating, The photosensitive resin composition for basic aqueous solution development of Claim 2.   The photosensitive resin composition for basic aqueous solution development according to any one of claims 1 to 3, wherein at least one of R1 and R2 in the formula (1 ") contains an aromatic group or a vinyl group. The photosensitive resin composition for basic aqueous solution development according to any one of claims 1 to 4, wherein the intramolecular cleavage reaction compound (A) is a compound (A1) represented by the following formula (1). .

(In the formula, R 1 and R 2 are each independently hydrogen or a monovalent organic group, and they may be the same or different. In addition, the two are bonded to form a cyclic structure. R3 and R4 are each independently hydrogen or a monovalent organic group, and they may be the same or different, and they may be combined to form a cyclic structure. good.)   The photosensitive resin composition for basic aqueous solution development according to claim 5, wherein at least one of R1 and R2 of the compound (A1) represented by the formula (1) is an aromatic group.   The terminal atom couple | bonded with the nitrogen atom among at least 1 of R3 and R4 of the compound (A1) represented by the said Formula (1) is a carbon atom which has SP3 orbital. Photosensitive resin composition for basic aqueous solution development.   At least one of R3 and R4 of the compound (A1) represented by the above formula (1) is selected from the group consisting of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. The photosensitive resin composition for developing a basic aqueous solution according to any one of claims 5 to 7, which is one or more selected aliphatic hydrocarbon groups.   The compound according to any one of claims 5 to 7, wherein R3 and R4 of the compound (A1) represented by the formula (1) are linked to form a cyclic structure together with nitrogen of a urethane bond structure. Photosensitive resin composition for basic aqueous solution development.   10. The intramolecular cleavage reaction compound (A) has absorption at at least one wavelength among electromagnetic waves having wavelengths of 436 nm, 405 nm, 365 nm, and 248 nm. Photosensitive resin composition for basic aqueous solution development.   The photosensitive resin composition for basic aqueous solution development according to any one of claims 1 to 10, comprising a sensitizer. The photosensitive resin composition for basic aqueous solution development according to any one of claims 1 to 11, 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 for basic aqueous solution development according to any one of claims 1 to 12 , 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 part of which is formed of the photosensitive resin composition according to any one of claims 1 to 13 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. The surface of the coating film or molded article made of a photosensitive resin composition according to any one of the claims 1 to 13, irradiating the electromagnetic wave in a predetermined pattern, the electromagnetic radiation portion of the coating film or molded body base A negative pattern forming method characterized by selectively reducing solubility in a basic aqueous solution and then developing using a basic aqueous solution. The negative pattern formation according to claim 15 , wherein after the irradiation with the electromagnetic wave, a heat treatment is performed to selectively reduce the solubility of the coating film or the molded body in the electromagnetic wave irradiation site in the basic aqueous solution. Method. The negative according to claim 16 , wherein after the irradiation with the electromagnetic wave, a heat treatment is performed before the development to selectively reduce the solubility of the coating film or molded body in the electromagnetic aqueous solution at the basic aqueous solution. Mold pattern forming method.

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