JPWO2010038837A1 - Photosensitive resin composition, article using the same, and negative pattern forming method - Google Patents

Abstract

Disclosed is a photosensitive resin composition that can obtain a high-sensitivity, solubility contrast regardless of the type of polyimide precursor and, as a result, can obtain a pattern having a good shape while maintaining a sufficient process margin. The photosensitive resin composition containing the photobase generator represented by general formula (I), and a polyimide precursor. (Each symbol is as defined in the specification.)

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 polyimide precursor, and in particular, a product or member formed through a patterning process using electromagnetic waves. Photosensitive 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 an article manufactured using the resin composition And a negative pattern forming method using the resin composition.

Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used as a surface protective film for semiconductor elements, an interlayer insulating film, and an insulating material for electronic components (Non-patent Document 1).
Circuit pattern formation on a semiconductor integrated circuit or printed circuit board is a complicated and diverse process such as film formation of a resist agent on the surface of the material, exposure to a predetermined location, removal of unnecessary portions by etching, etc., cleaning operation of the substrate surface, etc. Therefore, in order to simplify the manufacturing process of the circuit pattern, a heat-resistant photosensitive material that can be used by leaving a necessary portion of the resist as an insulating material after pattern formation by exposure and development is desired. ing. As these materials, heat-resistant photosensitive materials using polyimide as a base polymer have been proposed.

  As such photosensitive polyimide, for example, in Patent Document 1, a system composed of a polyimide precursor and dichromate was first proposed. However, this material has practical advantages such as high photosensitivity and high film forming ability, but lacks storage stability and has the disadvantage that chromium ions remain in polyimide. Did not come. Furthermore, in Patent Document 2, a compound in which a photosensitive group is introduced into a polyamic acid which is a polyimide precursor by an ester bond is added, and in Patent Document 3, an amine compound having a methacryloyl group is added to a polyamic acid in a polyimide precursor. A compound in which an amino group and a carboxyl group are ion-bonded has been introduced. However, the covalent bond type photosensitive polyimide represented by the ester bond has a problem in that the synthesis process is complicated and the cost is increased. In addition, the ion-bonded photosensitive polyimide has a problem that the bonding force between the polyimide skeleton and the photosensitive group is small and the exposed part is dissolved, so that the remaining film ratio is lowered and it is difficult to increase the film thickness. (Non-Patent Document 2). Many of these compounds are organic solvent developable, and in view of cost and environmental burden, compounds that can be developed with an alkaline aqueous solution are more desirable.

  Such a polyimide precursor uses an aromatic monomer as a basic skeleton so as to be excellent in heat resistance and mechanical properties. In general, a polyimide precursor having an aromatic ring as a basic skeleton has a broad absorption band in the ultraviolet-visible region having a wavelength of 400 nm or less, particularly in the wavelength region of i-line (wavelength: 365 nm) or less. Low translucency when irradiated with ultraviolet-visible light. For this reason, the photosensitive polyimide has a problem that the photochemical reaction does not proceed sufficiently in the exposed portion, and the sensitivity is low or the shape of the pattern is deteriorated. As the application range of heat-resistant photosensitive materials widens, material requirements are becoming increasingly diverse, and a thick film forming ability is required for photosensitive polyimide. When the formation pattern is a thick film, the problem of low light transmission becomes more serious. Therefore, in order to realize a heat-resistant photosensitive resin excellent in both film physical properties and sensitivity, in the g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm) region, Construction of a photosensitive system having photoreactive activity is indispensable, and in particular, construction of a photosensitive system having photoreactive activity in the g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) regions is desirable.

  In recent years, photobase generators have attracted attention as one of new pattern forming materials. For example, Non-Patent Document 3 discloses 2-nitrobenzyloxycarbonylcyclohexylamine as a photobase generator. However, since this compound has no sensitivity to h-rays, it is difficult to generate a base by h-rays.

  Patent Document 4 discloses a latent curable epoxy resin composition containing an epoxy resin and a compound having two or more groups represented by the following general formula in the molecule. However, Patent Document 4 only discloses that the epoxy resin composition is cured by light irradiation using an ultrahigh pressure mercury lamp and then heating.

（上記式においてＲは水素、アルキル基またはアリール基である。）

(In the above formula, R is hydrogen, an alkyl group or an aryl group.)

Further, Patent Document 5 discloses a resist forming material using 2-nitro-4,5-dimethoxybenzyloxycarbonylcyclohexylamine and a styrene-acrylic acid copolymer as a compound that generates a base. However, although the compound generating a base disclosed in Patent Document 5 has sensitivity to i-line, there is no description that it has sensitivity to h-line.
Patent Document 6 discloses a photosensitive resin composition containing a photobase generator and a polyimide precursor.

Japanese Patent Publication No.49-17374 Japanese Patent Publication No.55-30207 JP 54-145794 A Japanese Patent Publication No. 51-46159 Japanese Patent Laid-Open No. 6-345711 JP 2006-189591 A

“Latest Polyimide: Fundamentals and Applications”, ENTS, 2002, p. 327-338 “Latest Trends in Polymer Materials for Electronic Components III”, Sumibe Techno Research, 2004, p. 36-39 J. Am Chem. Soc., 1991, 113, p. 4303-4313

  In order to apply an existing photobase generator to a polyimide precursor system, there is a problem in terms of absorption wavelength. That is, many existing photobase generators have an absorption wavelength of 400 nm or less, and when added to a polyimide precursor as an imidization accelerator by photoreaction, the absorption wavelength of the polyimide precursor and the photobase generator overlaps. There is a problem with sensitivity. Furthermore, as shown in the comparative example described later, even if the existing photobase generator had an absorption wavelength of 400 nm or more, no photoreactive activity was observed in the wavelength region of 400 nm or more. . Therefore, in order to realize a heat-resistant photosensitive resin that is excellent in terms of heat resistance, mechanical properties, and sensitivity, a wavelength region of 400 nm or more, for example, g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) There is a need for a base generator having photoreactive activity in the region.

The present invention has been accomplished in view of the above circumstances, and a first object of the invention is high sensitivity, a solubility contrast can be obtained regardless of the type of polyimide precursor, and as a result, a sufficient process margin can be maintained. An object of the present invention is to provide a photosensitive resin composition capable of obtaining a pattern having a good shape.
The second object of the present invention is to provide a photosensitive resin composition having photoreactive activity in a wavelength region of 400 nm or more, for example, g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) region. It is in.

  The photosensitive resin composition according to the present invention contains a photobase generator represented by the general formula (I) and a polyimide precursor.

（上記一般式（Ｉ）において、Ｒ₁及びＲ₂はそれぞれ独立に置換基を有してもよい炭素数１〜１２のアルキル基または置換基を有してもよい炭素数６〜１２のアリール基を示し、Ｒ₁とＲ₂とが連結して置換基を有してもよい炭素数１〜２４のアルキレン基または置換基を有してもよい炭素数６〜２４のアリーレン基を形成してもよく、
Ｒ₃及びＲ₄はそれぞれ独立に水素原子、置換基を有してもよい炭素数１〜１２のアルキル基または置換基を有してもよい炭素数６〜１２のアリール基を示し、Ｒ₃およびＲ₄の少なくとも１つは水素原子ではなく、Ｒ₃とＲ₄とが連結してヘテロ原子を含んでも良い環状構造を形成してもよく、
Ｒ₅〜Ｒ₉はそれぞれ独立に水素原子、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数１〜１２のアルコキシ基、ハロゲン原子、シアノ基、アミノ基、炭素数１〜１２のアルキルアミノ基、炭素数１〜１２のアシルオキシ基、ニトロ基、又は炭素数１〜１２のアシル基を示す。）

(In the above general formula (I), R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms. R ₁ and R ₂ are linked to form an alkylene group having 1 to 24 carbon atoms which may have a substituent or an arylene group having 6 to 24 carbon atoms which may have a substituent. You can,
R ₃ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms, and R ₃ And at least one of R ₄ is not a hydrogen atom, but R ₃ and R ₄ may be linked to form a cyclic structure that may contain a hetero atom,
R _{5 to} R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, or a carbon number. An alkylamino group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms; )

The present inventors have shown that the N (α-aromatic substituted-2-nitro-4,5-dialkoxybenzyloxycarbonyl) amine compound represented by the above general formula (I) does not emit light in a wavelength region of 400 nm or more. It has been found that it can function as a photobase generator having reaction activity and can achieve a highly sensitive photosensitive polyimide by combining with a polyimide precursor.
In the photobase generator represented by the above formula (I) used in the present invention, the wavelength of light absorbed by the compound is increased by introducing an alkoxy group into the nitrobenzyl group by OR ₁ and OR ₂ . ing. Further, by introducing an aromatic group at the α-position of the nitrobenzyl group, the sensitivity to h rays is increased.
The photobase generator represented by the above formula (I) used in the present invention generates an amine, which is a basic substance, by radically cleaving the bond after radical hydrogen is extracted when irradiated with electromagnetic waves. Therefore, it acts as a very effective photosensitive component for the polyimide precursor whose reaction to the final product is promoted by the action of the base.

  Since the photobase generator has photoreactivity in the wavelength region of 400 nm or more by having the specific structure, an aromatic having a wide absorption band in the i-line (wavelength: 365 nm) region. The polyimide precursor having a ring as a basic skeleton functions as a highly sensitive photobase generator without overlapping the absorption wavelength. Therefore, according to the present invention, it is possible to increase the difference in solubility between an electromagnetic wave irradiation site and a non-irradiation site on the coating film or molded body of the photosensitive resin composition, and as a result, while maintaining a sufficient process margin, A pattern having a good shape can be obtained.

In the photosensitive resin composition of the present invention, in the photobase generator, R ₃ and R ₄ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent. R ₃ and R ₄ are preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, from the viewpoint of a large catalytic effect of the generated basic substance.
Further, in the photosensitive resin composition of the present invention, it is generated that the photobase generator generates a basic structure in which R ₃ and R ₄ are linked to form a cyclic structure which may contain a hetero atom. This is preferable because the catalytic effect of the substance is large.

In the photobase generator represented by the general formula (I), R ₁ and R ₂ are preferably methyl groups from the viewpoint of the amount of base generated per unit weight and the ease of production.

The polyimide precursor used in the photosensitive resin composition of the present invention is a compound that itself promotes the reaction to the final product by the action of a basic substance, and in particular, the final precursor by the action of a basic substance. It is preferable to use a polyimide precursor such as polyamic acid as the compound that promotes the reaction to the product and changes its solubility by heating. When such a polyimide precursor is used, a photosensitive polyimide resin composition excellent in heat resistance and mechanical properties can be obtained.
According to the present invention, it is possible to obtain a good pattern shape without applying a dissolution inhibitor or a dissolution inhibitor, even for a polyimide precursor that has conventionally been difficult to obtain a solubility contrast between an exposed area and an unexposed area. it can.

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

  In the photosensitive resin composition of the present invention, the 5% weight reduction temperature of the photobase generator is 170 ° C. or more, so that the imide is formed on the coating film of the photosensitive resin composition after exposure and before development. It is preferable because the photobase generator becomes difficult to decompose at the temperature of the conversion.

Moreover, since the photosensitive resin composition of the said invention can select the polyimide precursor of a wide structure, the hardened | cured material obtained by it has characteristically polyimides, such as heat resistance, dimensional stability, and insulation. Since the function can be imparted, it is suitable as a film, coating film or three-dimensional structure for all known members to which polyimide is applied.
In particular, the photosensitive composition according to the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film, for example, Suitable for forming color filters, flexible display films, semiconductor devices, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, other optical members, or building materials .

  Furthermore, the present invention provides a printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, a wiring coating, which is at least partially formed by the photosensitive resin composition according to the present invention or a cured product thereof. An article of any one of a covering film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, and a building material is provided.

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 reduce the solubility of the electromagnetic wave irradiation site of the coating film or molded product, and then developing.
In the said negative pattern formation method, the coating film which consists of a photosensitive resin composition by using together a polyimide precursor and a photobase generator as represented by the said Formula (I) as a photobase generator. Alternatively, it is possible to form a negative pattern for development without using a resist film for protecting the surface of the molded body from the developer.

As described above, according to the present invention, a polyimide precursor can be obtained using a novel photobase generator having photoreactive activity in g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) regions of 400 nm or more. A photosensitive polyimide resin composition can be prepared and used by a simple method of mixing an additive with the body. When the photobase generator represented by the above formula (I) is irradiated with electromagnetic waves, the hydrogen at the benzyl position is extracted, and then the bond is radically cleaved to generate an amine that is a basic substance. The present invention can be applied to polyimide precursors having various structures having a reaction that acts as a catalyst.
Therefore, the photosensitive resin composition according to the present invention can be selected from a wide range of final polyimide structures without being limited by the pattern formation process, and is excellent in heat resistance and mechanical properties. Available as a thing.
According to the present invention, a good pattern shape can be obtained without applying a dissolution inhibitor or a dissolution inhibitor for a polyimide precursor that has conventionally had difficulty in obtaining a solubility contrast between an exposed portion and an unexposed portion. .

FIG. 1 is a diagram showing transmittance curves of the filter 1 and the filter 2. FIG. 2 is a graph showing the relationship between the imidization ratio and the thermosetting temperature when the photosensitive resin composition is unexposed and after the exposure.

The present invention includes a photosensitive resin composition using a photobase generator, an article using the photosensitive resin composition, and a negative pattern forming method. Hereinafter, it demonstrates in order from the photosensitive resin composition.
In the present invention, the electromagnetic wave that cleaves the bond of the photobase generator as represented by the above formula (I) may be anything that can cause a hydrogen abstraction reaction, and visible and invisible regions. In addition to electromagnetic waves having a wavelength of, a particle beam such as an electron beam, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams are included.

  The photosensitive resin composition of the present invention contains a photobase generator represented by general formula (I) and a polyimide precursor.

（上記一般式（Ｉ）において、Ｒ₁及びＲ₂はそれぞれ独立に置換基を有してもよい炭素数１〜１２のアルキル基または置換基を有してもよい炭素数６〜１２のアリール基を示し、Ｒ₁とＲ₂とが連結して置換基を有してもよい炭素数１〜２４のアルキレン基または置換基を有してもよい炭素数６〜２４のアリーレン基を形成してもよく、
Ｒ₃及びＲ₄はそれぞれ独立に水素原子、置換基を有してもよい炭素数１〜１２のアルキル基または置換基を有してもよい炭素数６〜１２のアリール基を示し、Ｒ₃およびＲ₄の少なくとも１つは水素原子ではなく、Ｒ₃とＲ₄とが連結してヘテロ原子を含んでも良い環状構造を形成してもよく、
Ｒ₅〜Ｒ₉はそれぞれ独立に水素原子、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数１〜１２のアルコキシ基、ハロゲン原子、シアノ基、アミノ基、炭素数１〜１２のアルキルアミノ基、炭素数１〜１２のアシルオキシ基、ニトロ基、又は炭素数１〜１２のアシル基を示す。）

(In the above general formula (I), R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms. R ₁ and R ₂ are linked to form an alkylene group having 1 to 24 carbon atoms which may have a substituent or an arylene group having 6 to 24 carbon atoms which may have a substituent. You can,
R ₃ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms, and R ₃ And at least one of R ₄ is not a hydrogen atom, but R ₃ and R ₄ may be linked to form a cyclic structure that may contain a hetero atom,
R _{5 to} R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, or a carbon number. An alkylamino group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms; )

  The photobase generator represented by the above formula (I) used in the present invention generates an amine, which is a basic substance, by radically cleaving the bond after radical hydrogen is extracted when irradiated with electromagnetic waves. Let On the other hand, the polyimide precursor can lower the temperature at which the imidization reaction is initiated, for example, by the catalytic action of a basic substance. In other words, by allowing the polyimide precursor to coexist with the photobase generator and generating a base by irradiation with electromagnetic waves, the site irradiated with electromagnetic waves promotes the reaction to the final product of the polyimide precursor, and more Imidization can proceed at a low temperature. In order to obtain a pattern using the photosensitive resin composition of the present invention, for example, after irradiating an electromagnetic wave to a place where the pattern is to be left, imidization proceeds in a place where the basic substance is present, Heating is performed at a temperature where imidization does not proceed in a place where it does not exist. As a result, since the imidization proceeds only in the place where the basic substance exists, that is, the place irradiated with the electromagnetic wave and the solubility is lowered, by developing with a predetermined developer (organic solvent, alkaline aqueous solution, etc.), A pattern can be obtained. Then, according to the objective, it can heat further and can be set as a polyimide pattern.

The photobase generator represented by the above formula (I) used in the present invention has a wavelength of light absorbed by the compound, particularly when an alkoxy group is introduced into the nitrobenzyl group by OR ₁ and OR ₂ . It is getting longer. Further, by introducing an aromatic group at the α-position of the nitrobenzyl group, the sensitivity to h rays is increased. Thus, since the photobase generator used in the present invention has photoreactive activity in a wavelength region of 400 nm or more, an aromatic ring having a wide absorption band in the i-line (wavelength: 365 nm) region is used. Since it functions as a high-sensitivity photobase generator without overlapping the absorption wavelength with the polyimide precursor in the basic skeleton, between the electromagnetic wave irradiation site and the non-irradiation site on the coating film or molded body of the photosensitive resin composition As a result, a pattern having a good shape can be obtained while maintaining a sufficient process margin.

First, the photobase generator represented by the general formula (I) will be described. The photobase generator means a substance that decomposes its chemical structure upon irradiation with light and generates a basic substance.
<For R ₁ and R _2>
In the general formula (I), R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms. R ₁ and R ₂ are linked to form an alkylene group having 1 to 24 carbon atoms which may have a substituent or an arylene group having 6 to 24 carbon atoms which may have a substituent. An annular structure may be formed. OR ₁ and OR ₂ constitute an alkoxy group, and by introducing such an alkoxy group into the nitrobenzyl group, the compound represented by the general formula (I) can increase the wavelength of light to be absorbed. it can. As a result, the compound represented by the general formula (I) used in the present invention can generate a base by absorbing h rays.

Among the alkyl groups having 1 to 12 carbon atoms that may have a substituent, the alkyl group having 1 to 6 carbon atoms that may have a substituent from the viewpoint of the amount of base generated per unit weight and the ease of production. Group is preferable, and an alkyl group having 1 to 3 carbon atoms which may have a substituent is more preferable. Examples of the substituent include a methoxy group, a phenyl group, and a 2-thioxanthyl group.
Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. Can do. Among these, a methyl group, an ethyl group, and particularly a methyl group is preferable from the viewpoint of the amount of base generated per unit weight. In addition, in this invention, carbon number of "the C1-C12 (1-6, 1-3) alkyl group which may have a substituent" is carbon number of an alkyl group part, The number of carbon atoms is not included.
Among the aryl groups having 6 to 12 carbon atoms which may have a substituent, an aryl group having 6 carbon atoms which may have a substituent from the viewpoint of the amount of base generated per unit weight and the ease of production. preferable. As an example of the said substituent, the thing similar to what was mentioned by description of a C1-C12 alkyl group which may have a substituent is mentioned.
Examples of the aryl group having 6 to 12 carbon atoms which may have a substituent include a phenyl group, a naphthyl group, and a toluyl group. In the present invention, the carbon number of the “aryl group having 6 to 12 carbon atoms (6) which may have a substituent” is the carbon number of the aryl group portion, and does not include the carbon number in the substituent. Shall.
In addition, R ₁ and R ₂ may be linked to form an alkylene group or an arylene group to form a cyclic structure, and a substituent may be bonded on this ring. Examples of the substituent include a methyl group, an ethyl group, a methoxy group, and a phenyl group. Examples of the group composed of R ₁ and R ₂ when R ₁ and R ₂ are linked to form a cyclic structure include a methylene group, an ethylene group, a 1,3-propylene group, and 1,2-phenylene. Group and the like. In the present invention, the carbon number of the “optionally substituted alkylene group having 1 to 24 carbon atoms” and the “optionally substituted aryl group having 6 to 24 carbon atoms” is alkylene. It is the carbon number of the group and the arylene group part, and does not include the carbon number in the substituent.

<For R ₃ and R _4>
In the general formula (I), R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an optionally substituted carbon group having 6 carbon atoms. ~ 12 aryl groups, wherein at least one of R ₃ and R ₄ is not a hydrogen atom, but R ₃ and R ₄ may be linked to form a cyclic structure that may contain a hetero atom. . At least one of R ₃ and R ₄ is not a hydrogen atom. However, if both are hydrogen atoms, the compound is not stable, and the generated amine is also ammonia, which is useful as a base generator. Because there is no.

By changing the number of hydrogen atoms introduced at the positions of R ₃ and R ₄ and the type of the substituent, it is possible to change the physical properties of the amine, such as basicity, thermal properties, and solubility. The amine having higher basicity has a stronger catalytic effect on the dehydration condensation reaction in the imidation of the polyimide precursor described below, for example, and the catalytic effect in the dehydration condensation reaction at a lower temperature can be reduced by adding a smaller amount. Expression is possible. That is, even when the sensitivity of the compound represented by the above formula (I) to the electromagnetic wave itself is low, the apparent sensitivity as the photosensitive resin composition is improved because the generated basic substance has a large catalytic effect.
The basic substance generated by the cleavage reaction accompanying the electromagnetic wave absorption of the compound represented by the above formula (I) is a fat because the effect of the generated basic substance such as the catalytic effect is large. Group amines are preferred. Among these, secondary aliphatic amines are preferable from the viewpoint of basicity. However, even when an aliphatic primary amine is used, a sufficient catalytic effect can be obtained as compared with the case where an aromatic amine is used. Therefore, among aliphatic amines, from the viewpoints of thermal properties such as 5% weight loss temperature, 50% weight loss temperature, thermal decomposition temperature, other physical properties such as solubility, ease of synthesis and cost, etc. It is desirable to select as appropriate.

R ₃ and R ₄ may have a hydrogen atom or a substituent from the viewpoint of generating such an aliphatic amine, achieving high sensitivity, and increasing the solubility contrast of the unexposed area. It is preferably a good alkyl group having 1 to 12 carbon atoms (except when both R ₃ and R ₄ are hydrogen atoms). Especially, it is preferable that R < ₃ > and R < ₄ > is a C1-C12 alkyl group which may have a substituent.
Examples of the alkyl group having 1 to 12 carbon atoms which may have such a substituent include an alkyl group composed of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, or a combination thereof. In addition, the said alkyl group may have substituents, such as an aromatic group, or may contain bonds other than hydrocarbons, such as a hetero atom, in a hydrocarbon chain. For example, a linear or branched saturated or unsaturated alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, Examples thereof include a hydroxyalkyl group having 1 to 12 carbon atoms.

  Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, ethynyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, cyclohexyl group, isobornyl group, norbornyl group. , An adamantyl group, a benzyl group and the like, but are not limited thereto.

R ₃ and R ₄ may be connected to form a cyclic structure, or may be connected to each other to form a heterocyclic structure containing a nitrogen atom to which R ₃ and R ₄ are bonded. May be. Such a case is also preferable in view of the large catalytic effect of the generated basic substance.
Such is annularly two of R ₃ and R ₄ linked, the heterocyclic structure when forming a heterocyclic structure containing a nitrogen atom and R ₃ and R ₄ are attached, for example, Aziridine (3-membered ring), azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring), azepan (7-membered ring), azocane (8-membered ring) and the like. Furthermore, the cyclic structure may contain a hetero atom in addition to the nitrogen atom to which R ₃ and R ₄ are bonded. Examples of such a heterocyclic structure include morpholine, thiomorpholine, oxazolidine, thiazolidine and the like. Can be mentioned. These heterocyclic structures may have a substituent such as a linear or branched alkyl group, for example, as an alkyl substituent, a monoalkylaziridine such as methylaziridine, a dialkylaziridine such as dimethylaziridine, methylazetidine, etc. Dialkyl azetidine such as monoalkyl azetidine, dimethyl azetidine, trialkyl azetidine such as trimethyl azetidine, monoalkyl pyrrolidine such as methyl pyrrolidine, dialkyl pyrrolidine such as dimethyl pyrrolidine, trialkyl pyrrolidine such as trimethyl pyrrolidine, tetramethyl Tetraalkylpyrrolidines such as pyrrolidine, monoalkylpiperidines such as methylpiperidine, dialkylpiperidines such as dimethylpiperidine, trialkylpiperidines such as trimethylpiperidine Jin, tetraalkyl piperidine such as tetramethylpiperidine, penta-alkyl piperidines such as such as pentamethyl piperidine.

Among the alkyl groups having 1 to 12 carbon atoms that may have a substituent, the alkyl group having 1 to 8 carbon atoms that may have a substituent from the viewpoint of the amount of base generated per unit weight and the ease of production. Group is preferable, and an alkyl group having 1 to 6 carbon atoms which may have a substituent is more preferable. Examples of the substituent are the same as those described in the description of the alkyl group having 1 to 12 carbon atoms which may have a substituent of R ₁ and R ₂ .
In addition, from the viewpoint of the amount of base generated per unit weight and ease of production, the heterocyclic structure which may have the above substituent preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. It is preferable. In this case, the substituent is preferably a linear or branched alkyl group.

Examples of the aryl group having 6 to 12 carbon atoms that may have a substituent include those mentioned in the description of the alkyl group having 1 to 12 carbon atoms that may have a substituent for R ₁ and R _2. The same thing is mentioned.

<For R ₅ ~R _9>
In the general formula (I), R _{5 to} R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, A cyano group, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms is shown.
In the present invention, introduction of an aromatic group at the α-position of the nitrobenzyl group increases the sensitivity to h-rays. Therefore, all of R _{5 to} R ₉ may be hydrogen atoms.

The aromatic substituents R _{5 to} R ₉ can be introduced by selecting the type of the substituent relatively freely from the viewpoint of improving the sensitivity or adjusting the absorption wavelength. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polyimide precursor to be combined. For example, the absorption wavelength can be shifted to the longer wavelength side by bonding of an aromatic substituent. The degree of shift (shift value) varies depending on the type of substituent. For this shift value, the table described in “Identification Method by Spectrum of Organic Chemistry 5th Edition (RMSilverstein, 281, published by Tokyo Chemical Dojin)” is a reference.

Among the alkyl groups having 1 to 12 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable from the viewpoint of the amount of base generated per unit weight and ease of production. Examples of alkyl group having 1 to 12 carbon atoms include the same as those exemplified in the description of R ₃ and R _4.

Among the aryl groups having 6 to 12 carbon atoms, aryl groups having 6 carbon atoms are preferable from the viewpoint of the amount of base generated per unit weight and ease of production. Examples of the aryl group having 6 to 12 carbon atoms which may have a substituent include the same groups as those exemplified for R ₁ and R ₂ above.
Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group and an ethoxy group.
Examples of the halogen atom include a chlorine atom and a bromine atom.
Examples of the alkyl of the alkylamino group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group.
Examples of the acyloxy group having 1 to 12 carbon atoms include an acetoxyl group and a propionyloxy group.
As an example of the said C1-C12 acyl group, the aroyl group containing aromatic groups, such as a benzoyl group other than a formyl group and an acetyl group, is mentioned.

  Examples of the photobase generator represented by the general formula (I) include, but are not limited to, those represented by the following chemical formula.

  The compound of the present invention can be produced, for example, by a method using a carbon nucleophile such as the Grignard reaction. Specifically, after reacting an aldehyde compound represented by the following general formula (II) with an aromatic compound represented by the following general formula (III), the product is isolated or isolated It can manufacture by making the compound represented with the following general formula (IV) react.

In the general formula (II), R ₁ and R ₂ are the same as R ₁ and R ₂ in the general formula respectively (I).
The general formula (III), is the same as R ₅ to R ₉ in R ₅ to R ₉ are each the formula (I), M is a substituent containing a metal, the metal, Mg, Zn Li, Sn or Cu. Examples of M include those in which a halogen atom or an alkoxy group is coordinated to the metal. Specific examples of M include Li, MgCl, MgBr, and ZnCl.
The general formula (IV), is the same as R ₃ and R ₄ in the R ₃ and R ₄ each general formula (I), X is fluorine, chlorine, bromine, a principal halogen atom selected from iodine.

  A specific example of this reaction is by reacting 2-nitro-4,5-dimethoxybenzaldehyde with phenylmagnesium bromide and then with or without morpholine carbonyl chloride. A reaction for obtaining α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonylmorpholine can be mentioned.

  As another method, a carbinol compound represented by the following general formula (VI) is reacted with a compound represented by the following general formula (IV) or an isocyanate compound represented by the following general formula (V). Can be manufactured.

In the general formula (VI), R ₁ and R ₂ are the same as R ₁ and R ₂ in the general formula respectively (I), R in R ₅ to R ₉ each Formula (I) ₅ to R _Same as ₉ . The compound represented by the general formula (VI) can be obtained by reacting the aldehyde compound represented by the general formula (II) described above with the aromatic compound represented by the general formula (III). In addition, it can be synthesized by a known method. For example, it can be synthesized by the method described in Tetrahedron, 63, (2007), 474, and Molecules, 1999, 4, M113.
In the general formula (IV), R ₃ and R ₄ are each same as R ₃ and R ₄ in the general formula (I).
In the above general formula (V), R ₄ is the same as R ₄ in formula (I).

  Furthermore, as another method, the compound of the present invention is obtained by reacting a carbinol compound represented by the following general formula (VI) with a carbonyl compound represented by the following general formula (VII), It can be produced by synthesizing an ester compound represented by (VIII) and reacting this ester compound with an amine compound represented by the following general formula (IX). In this case, after isolating an ester compound formed by reacting the carbinol compound with a carbonyl compound represented by the following general formula (VII), the ester compound is reacted with an amine compound represented by the general formula (IX). The reaction may be carried out without isolation.

The general formula (VI) and the general formula (VIII), R ₁ and R ₂ are each same as R ₁ and R ₂ in the general formula (I), R ₅ ~R ₉ each Formula (I It is the same as R _{5 to} R _{9 in} ).
In the general formula (VII), Z represents a chlorine atom, a bromine atom, an iodine atom, a trichloromethoxy group, or a 1-imidazolyl group.
In the general formulas (VII) and (VIII), R ₁₀ is a chlorine atom, a trichloromethoxy group, a 1-imidazolyl group, a phenoxy group, a 4-nitrophenoxy group, or a 4-cyanophenoxy group.
Such a compound represented by the general formula (VII) includes phosgene, chlorobenzene because R ₁₀ easily acts as a leaving group when reacted with the above general formula (IX) and is industrially available. Trichloromethyl formate, triphosgene, carbonyldiimidazole, chloroformate-p-nitrophenyl and chloroformate-p-cyanophenyl are preferred.
Similarly, the general formula (IX), R ₃ and R ₄ are each same as R ₃ and R ₄ in the general formula (I).
According to this method, even when it is difficult to obtain a compound represented by the above general formula (IV) for introducing an amine, a desired corresponding secondary amine type compound of the present invention can be synthesized. .

  Examples of the basic substance generated during the decomposition of the photobase generator represented by the formula (I) include primary amines such as n-butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, amantadine, and benzylamine, Linear secondary amines such as diethylamine, dipropylamine, diisopropylamine, dibutylamine, and the like, secondary secondary amines such as aziridines, azetidines, pyrrolidines, piperidines, azepanes, azocans, and alkyl substitutions thereof. Secondary amines and the like. Examples of the basic substance having a heterocyclic structure containing a hetero atom in addition to the nitrogen atom include morpholine, thiomorpholine, oxazolidine, thiazolidine and the like.

  The basic substance produced by the photodecomposition reaction of the photobase generator represented by the formula (I) and the photobase generator represented by the formula (I) of the present invention is the photobase generator of the present invention. It is preferable that the coating film of the photosensitive resin composition contained does not decompose at the heating temperature (temperature for partial imidization for pattern formation) performed after exposure and before development. Specifically, the temperature when the photobase generator represented by the above formula (I) or the basic substance produced by the photolysis reaction is heated to reduce 5% weight from the initial weight (5% weight reduction) The temperature is preferably 170 ° C., more preferably 200 ° C. or higher.

  Furthermore, when the photosensitive resin composition containing the photobase generator of the present invention is used as a product, it is preferable that the basic substance does not remain in the photosensitive resin composition. A basic substance that decomposes or volatilizes in the (complete imidization process) is preferable. Specifically, it is preferable that the temperature (50% weight reduction temperature) when the basic substance generated by the photolysis reaction is heated to reduce 50% weight from the initial weight is 400 ° C. or less.

Typical emission wavelengths of a high-pressure mercury lamp, which is a general exposure light source, are 436 nm, 405 nm, and 365 nm, but a polyimide precursor having an aromatic ring as a basic skeleton has a wide absorption band at 365 nm Therefore, it is preferable that the photobase generator represented by the formula (I) of the present invention has absorption of electromagnetic waves having a wavelength of 400 nm or more.
This is because when the photobase generator has absorption of an electromagnetic wave having a wavelength of 400 nm or more, the sensitivity can be improved without the absorption wavelengths of the polyimide precursor and the photobase generator overlapping. From the viewpoint of using a typical emission wavelength of a high-pressure mercury lamp, which is a general exposure light source, it is preferable that the photobase generator has an absorption at least at one of electromagnetic waves having wavelengths of 436 nm and 405 nm. .

Moreover, it is preferable that the photobase generator represented by the formula (I) of the present invention has photodegradability with respect to electromagnetic waves having a wavelength of 400 nm or more, and further 400 nm to 500 nm.
Above all, the photobase generator not only absorbs at least one of electromagnetic waves having wavelengths of 436 nm and 405 nm, but also has photodegradability with respect to electromagnetic waves of at least one wavelength of 436 nm and 405 nm. Is preferred. In some cases, even if absorption occurs in at least one wavelength of electromagnetic waves having wavelengths of 436 nm and 405 nm, the electromagnetic waves having such wavelengths may not be photodegradable.
Whether or not it has photodegradability with respect to electromagnetic waves having a wavelength of 405 nm or more is determined by, for example, irradiating the photobase generator using a high-pressure mercury lamp through a filter that does not pass i-line (wavelength: 365 nm) or less. Thus, it can be determined by observing whether the photobase generator is decomposed or whether a basic substance is generated. Similarly, whether it has photodegradability with respect to electromagnetic waves having a wavelength of 436 nm or more can be determined by, for example, using a high-pressure mercury lamp through a filter that does not pass a wavelength of h line (wavelength: 405 nm) or less as a photobase generator It can be determined by irradiating and observing whether the photobase generator is decomposed or whether a basic substance is generated.

Next, the polyimide precursor will be described.
The polyimide precursor used in the present invention is preferably soluble in any solvent (organic solvent or aqueous solution). If it is soluble in a solvent (an organic solvent or an aqueous solution), the solubility of the polyimide precursor in the solvent is changed, and the soluble solvent is used as a developer. It is possible to perform development with a neutral aqueous solution, an acidic aqueous solution, or a neutral aqueous solution.
Here, the term “soluble in a solvent” specifically means that the dissolution rate of the coating film formed on the substrate at 25 ° C. in the solvent is 100 Å / sec or more. The dissolution rate is more preferably 1000 kg / sec or more.
For example, what is soluble in a basic aqueous solution is specifically that the dissolution rate of a coating film formed on a substrate in a 0.1 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. It is more than sec. 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 solvent is preferably 100 Å / sec or more, more preferably 1000 Å / sec or more, at 25 ° C. preferable.

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

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 the post-process (usually the heating process) 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 polyimide precursor whose reaction to the final product is promoted by the action of a basic substance is used. Here, in the aspect in which the reaction to the final product is promoted by the action of the basic substance, the polyimide precursor is not only the form in which the polyimide precursor is changed to the final product only by the action of the basic substance, A mode is included in which the reaction temperature of the polyimide precursor to the final product is lowered by the action of the basic substance as compared with the case where the action of the basic substance is absent.
If there is a difference in reaction temperature depending on the presence or absence of such a basic substance, the reaction temperature difference can be used at an appropriate temperature at which only the polyimide precursor coexisting with the basic substance reacts with the final product. By heating, only the polyimide precursor coexisting with the basic substance reacts with the final product, and the solubility in the solvent changes. Therefore, the solubility of the polyimide precursor in a certain solvent can be changed depending on the presence or absence of the basic substance, and consequently, patterning by development using the solvent as a developer becomes possible. Therefore, as the polyimide precursor used in the present invention, a polyimide precursor whose reaction to the final product is promoted by the action of a basic substance and whose solubility changes lower than before heating is suitable. Used for.

  Here, as the polyimide precursor, a polyamic acid represented by the following formula (X) is preferably used.

（式（Ｘ）中、Ｒ^１１は４価の有機基である。Ｒ^１２は２価の有機基である。）

(In formula (X), R ¹¹ is a tetravalent organic group. R ¹² is a divalent organic group.)

Incidentally, tetravalent R ¹¹ represents only valence for bonding with the acid, but may have further substituents other. Similarly, the divalent value of R ¹² indicates only the valence for bonding with the amine, but may have other substituents.
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 polyimide precursor whose thermosetting temperature is lowered by the catalytic action of a base, such as a polyamic acid, first, a photosensitive resin composition in which such a polyamic acid is combined with the photobase generator is applied. Irradiate an electromagnetic wave to the portion of the film or molded body where the pattern is to be left. Then, a basic substance is generated in the irradiated portion, and the imidization temperature of that portion is selectively lowered. Next, the irradiated part undergoes an imidization reaction, while the non-irradiated part is heated at a processing temperature at which the imidization reaction does not occur, and only the irradiated part is partially imidized to the extent that it does not dissolve in the developer. 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 imidization. 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 compound represented by the above formula (I) functions as a high-sensitivity photobase generator, and an electromagnetic wave irradiation site and a non-irradiation site on the coating film or molded body of the photosensitive resin composition. Therefore, even when a basic aqueous solution is used instead of an organic solvent, excellent developability can be obtained.
As a secondary effect, when the polyimide precursor to be used is a polyamic acid, it is sufficient that the temperature required for imidization is low due to the catalytic effect of the basic substance. It can be lowered to below ℃. 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 technique 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 methylcyclobutane tetracarboxylic dianhydride. , Aliphatic tetracarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′ , 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 , 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride , Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1, 1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, , 3-bis [( , 4-Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2- Dicarboxy) phenoxy] phenyl} propane dianhydride,

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

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

  On the other hand, the amine component can also be used alone or in combination of two or more diamines. The diamine component used is not limited, 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 Like 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane Aromatic amines;

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

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

（ａは１以上の自然数、アミノ基はベンゼン環同士の結合に対して、メタ位または、パラ位に結合する。）

(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.)

Further, in the above formula (XI), 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 less can be improved by introducing fluorine as a substituent of the aromatic ring.

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

On the other hand, in order to synthesize a polyimide precursor, for example, while cooling a solution in which 4,4′-diaminodiphenyl ether as an amine component is dissolved in an organic polar solvent such as N-methylpyrrolidone, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is gradually added and stirred to obtain a polyimide precursor solution.
The polyimide precursor synthesized in this way has a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide obtained is required to have heat resistance and dimensional stability. Is preferred. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure The proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and particularly preferably 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 thickness of at least 5% with respect to the exposure wavelength when the film thickness is 5 μm. It preferably exhibits a transmittance, and more preferably exhibits a transmittance of 15% or more.
That the transmittance | permeability of a polyimide precursor is high with respect to an exposure wavelength means that there is little loss of light, and a highly sensitive photosensitive resin composition can be obtained.

In addition, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a transmittance with respect to an electromagnetic wave having a wavelength of at least 436 nm, 405 nm, and 365 nm is formed on a film having a thickness of 5 μm. Is preferably 5% or more, more preferably 15%, and still more preferably 50% or more.
Among them, from the point of combination with the photobase generator according to the present invention, the transmittance with respect to an electromagnetic wave having a wavelength of 405 nm is preferably 5% or more, more preferably 15%, even more preferably when formed on a film having a thickness of 5 μm. Preferably it is 50% or more.

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 or the like is performed to obtain a polymer such as polyimide. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases and the solubility decreases, so that it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.
The molecular weight used here refers to a value in terms of polystyrene by gel permeation chromatography (GPC), may be the molecular weight of the polyimide precursor itself, or after chemical imidization treatment with acetic anhydride or the like. Things can be used.

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

The photosensitive resin composition according to the present invention may be a simple mixture of the photobase generator, the polyimide precursor, and a solvent, but further, a sensitizer, a light or thermosetting component, A photosensitive resin composition may be prepared by blending a non-polymerizable binder resin other than the polyimide precursor and other components.
Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition. Moreover, when using a polyamic acid as a polyimide precursor, you may use the solution obtained by the synthesis reaction of the polyamic acid as it is, and mix other components there as needed.

When there is a portion where the absorption wavelength of the photobase generator overlaps with the absorption wavelength of the polyimide precursor and sufficient sensitivity cannot be obtained, addition of a sensitizer may be effective as a means for improving sensitivity. . Further, even when the photobase generator has an absorption wavelength in the wavelength band of electromagnetic waves that pass through the polyimide precursor, a sensitizer can be added as a means for improving sensitivity. However, it is necessary to take into consideration the film physical properties of the resulting pattern, particularly the decrease in film strength and heat resistance, accompanying the decrease in the content of the polyimide precursor due to the addition of a sensitizer.
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.
In the present invention, one or more of these sensitizers can be used.

Examples of the solvent used in the composition include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether, ethylene glycol Glycol monoethers (so-called cellosolves) such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; ethyl acetate, acetic acid Chill, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, Esters such as dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, Halogenated hydrocarbons such as 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N- Amides such as methylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide; Pyrrolidones such as N-methylpyrrolidone; Lactones such as γ-butyrolactone; Sulfoxides such as dimethylsulfoxide And other organic polar solvents, and aromatic hydrocarbons such as benzene, toluene, and xylene, and other organic nonpolar solvents. These solvents are used alone or in combination.
Among them, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexa Polar solvents such as methylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone It is mentioned as a suitable thing.

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

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

  In order to impart processing characteristics and various functionalities to the resin composition according to the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles 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 polyimide precursor (solid content) is obtained from the film properties of the pattern obtained, particularly from the viewpoint of film strength and heat resistance, with respect to the entire solid content of the photosensitive resin composition, It is preferable to contain 30% by weight or more and 50% by weight or more. Moreover, the photobase generator represented by the formula (I) is usually 0.01 to 50 parts by weight, preferably 0 with respect to 100 parts by weight of the solid content of the polyimide precursor contained in the photosensitive resin composition. It is preferable to make it contain in the range of 0.1-30 weight part. If it is less than 0.01 part by weight, the effect of promoting cyclization reaction tends to be insufficient, and if it exceeds 50 parts by weight, it becomes difficult to satisfy various physical properties required for the finally obtained resin cured product.
Moreover, it is preferable to set it as less than 50 weight part with respect to 100 weight part of solid content of a polyimide precursor, and, as for the compounding quantity of the said sensitizer, it is more preferable to set it as less than 30 weight part. Further, in order to prevent deterioration of various physical properties required for the finally obtained resin cured product, the total of the photobase generator and the sensitizer represented by the formula (I) according to the present invention is 100% by weight of the polyimide precursor. The amount is desirably 50 parts by weight or less with respect to parts.
The mixing ratio of other optional components is preferably in the range of 0.1% by weight to 20% by weight with respect to the entire solid content of the photosensitive resin composition. If it is less than 0.1% by weight, the effect of adding the additive is difficult to be exhibited, and if it exceeds 20% by weight, the properties of the finally obtained resin cured product are hardly reflected in the final product. In addition, solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

  The photosensitive resin composition according to the present invention can be used in various coating processes and molding processes to produce films and molded articles having a three-dimensional shape.

The polyimide obtained from the photosensitive resin composition of the present invention is satisfactory 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 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 obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance. However, in applications where a thermoforming process is considered, such as an optical waveguide, 120 ° C. to 450 ° C. It is preferable to show a glass transition temperature of about ° C, and 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 (E ″)) by dynamic viscoelasticity measurement when the polyimide obtained from the photosensitive resin composition can be formed into a film shape. / Storage elastic modulus (E ′)) is determined from the peak temperature. 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 obtained from the photosensitive resin composition cannot be formed into a film shape, the determination is made based on the temperature at the inflection point of the baseline of the differential thermal analyzer (DSC).

From the viewpoint of the dimensional stability of the polyimide 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 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. It is done.

As described above, the photosensitive polyimide resin composition according to the present invention has a wide variety of polyimide precursors because the compound represented by the above formula (I) functions as a highly sensitive photobase generator. The structure of the polyimide finally obtained can be selected from a wide range.
In addition, according to the present invention, a photosensitive polyimide resin composition can be obtained by a simple method of simply mixing a photobase generator represented by the formula (I) according to the present invention with a polyimide precursor. Excellent cost performance.
Furthermore, due to the catalytic effect of the amine generated by the irradiation of electromagnetic waves, the processing temperature required for the reaction to the final product such as imidization can be reduced, thereby reducing the inability to process and damage to the product due to heat. Is possible.

  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. It is preferably used as a material for forming semiconductor devices, electronic parts, interlayer insulating films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members, or building materials. Specific examples include buffer coating films for semiconductor devices, interlayer insulating films of multilayer wiring boards, and the like.

  In particular, the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film made of polyimide. Suitable for forming color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, other optical members or electronic members, for example ing.

  Further, in the present invention, a printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, which is at least partly formed by the photosensitive resin composition according to the present invention or a thermoset thereof, An article of any one of a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, and a building material is provided.

Next, the negative pattern forming method according to the present invention will be described.
In the negative pattern forming method according to the present invention, the surface of the coating film or molded body comprising the photosensitive resin composition according to the present invention is irradiated with electromagnetic waves in a predetermined pattern, and if necessary after heat treatment or the like. It develops, after processing, selectively reducing the solubility of the electromagnetic wave irradiation site | part of the said coating film or a molded object, It is characterized by the above-mentioned.
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 photobasic substance is decomposed and a basic substance is generated only in the exposed portion. The basic substance acts as a catalyst that promotes the reaction of the polyimide precursor in the exposed area to the final product.

  When the basic substance reacts directly with the polyimide precursor of the exposed part to the final product and only the polyimide precursor of the exposed part is selectively reduced in solubility in a certain solvent, It is possible to perform development by dissolving only the unexposed part where the solubility is not lowered without using post-processing and using the solvent having the lowered solubility of the exposed part as a developer.

  The photosensitive resin composition of the present invention includes N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N- Dimethyl methoxyacetamide, dimethyl sulfoxide, hexamethylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl- After being dissolved in a polar solvent such as γ-butyrolactone, it is applied to the surface of a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by dipping, spraying, screen printing, spin coating, etc. Removing part More, it is possible to provide a tack-free coating on the substrate surface. Although there is no restriction | limiting in particular in the thickness of a coating film, it is preferable that it is 0.5-50 micrometers, and it is more desirable that it is 1.0-20 micrometers from a sensitivity and a development speed surface. As drying conditions of the apply | coated coating film, 80-100 degreeC and 1 minute-20 minutes are mentioned, for example.

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

  The exposure method and exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure, and may be a g-line stepper, an i-line stepper, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, Alternatively, a projector or a radiation source that can irradiate other ultraviolet rays, visible rays, X-rays, electron beams, or the like 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 an electromagnetic wave irradiation site of the coating film or molded body in a certain solvent.
The post-treatment such as heat treatment is, for example, a treatment in which only the polyimide precursor in the exposed portion coexisting with the basic substance is reacted with the final product. Therefore, when heat treatment is performed, for example, it may be performed at a temperature at which the cyclization rate of the polyimide precursor becomes different between the exposed portion where the basic substance is present and the unexposed portion where the basic substance is not present. preferable.

For example, when polyamic acid is imidized, the preferable temperature range of the heat treatment at this stage is usually about 60 ° C to 200 ° 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, if the heat treatment temperature is 200 ° 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 exists. Due to the progress of imidization, a difference in solubility between the exposed portion and the unexposed portion is difficult to occur.
Specifically, for example, heating is performed at 120 to 200 ° C. for 1 minute to 20 minutes.
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 developer used in the development step is not particularly limited, and can be appropriately selected according to the polyimide precursor to be used, such as a basic aqueous solution or an organic solvent.
The basic aqueous solution is not particularly limited. For example, in addition to an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.01% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight, diethanolamine is used. , Diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, Examples include aqueous solutions of cyclohexylamine, ethylenediamine, hexamethylenediamine, tetramethylammonium, and the like.
The solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.
The organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, Add alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of two or more. May be. After development, wash with water. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.

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

[Synthesis Example 1]
2-Nitro-4,5-dimethoxybenzaldehyde (10.9 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 ml of anhydrous tetrahydrofuran, cooled to 0 ° C. with stirring in a nitrogen stream, and 50 ml of a phenylmagnesium bromide tetrahydrofuran solution ( 1 mol / L Aldrich) was added dropwise over 15 minutes.
After completion of the dropwise addition, 7.51 g of cyclohexyl isocyanate (Tokyo Kasei Reagent) was added to the reaction solution at room temperature, stirred for 5 hours, and left overnight.
The next day, an aqueous solution (using 100 ml of water) in which 3.2 g of ammonium chloride was dissolved was added and stirred for 10 minutes, followed by extraction with ethyl acetate. The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution, washed with water, and concentrated with an evaporator. As a result, a pale yellow solid was obtained. The obtained solid was purified by column chromatography using a mixed solvent of hexane and ethyl acetate, and the fraction was concentrated to give N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylamine. 1.2 g of slightly yellow crystals of (photobase generator 1) was obtained.

It was confirmed by ¹ H-NMR that this crystal was N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylamine represented by the following formula. (1.0-2.0 ppm m 10H —CH 2 —, 3.5 ppm m 1H —CH—N, 3.9 ppm s 6H OCH 3, 4.7 ppm d 1H NH, 7.1 ppm s 1H CH—O, 7.2 -7.7 ppm 7H aromatic CH)

[Synthesis Example 2]
N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) morpholine (photobase generation) was carried out in the same manner as in Example 1 except that 7.5 g of morpholine carbonyl chloride was used instead of cyclohexyl isocyanate. 9.6 g of slightly yellow crystals of agent 2) were obtained.
It was confirmed by ¹ H-NMR that this crystal was N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) morpholine represented by the following formula. (3.4-3.7 ppm 8H OCH2CH2N, 3.9 ppm 6H OCH3, 6.9 ppm s 1H CH-O, 7.2-7.7 ppm 7H aromatic CH)

[Synthesis Example 3]
In a 100 ml two-necked flask, 1.25 g of N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylamine synthesized in Synthesis Example 1, tetrahydrofuran (19.8 ml) and dimethylformamide (2. 0 ml) was added and dissolved. While cooling with ice, 0.144 g of sodium hydride was added. Thereafter, methyl iodide (0.56 ml) was added, and the mixture was stirred at 0 ° C. for 10 minutes, followed by heating under reflux for 7 hours. Upon cooling, a solid precipitated, so 10 ml of dimethylformamide was added and dissolved, and the reaction solution was poured into a 10 wt% aqueous hydrochloric acid solution (22 ml). Ethyl acetate (22 ml) was added for extraction, the organic layer was dehydrated over anhydrous magnesium sulfate, and the resulting solid was purified using silica gel chromatography to obtain N- (α-phenyl-2-nitro-4,5- 0.76 g of a pale yellow solid of dimethoxybenzyloxycarbonyl) cyclohexylmethylamine (photobase generator 3) was obtained. It was identified by ¹ H-NMR that the obtained solid was N- (α-phenyl-2-nitro-4,5-dimethoxybenzyloxycarbonyl) cyclohexylmethylamine represented by the following formula. (1.0-2.0 ppm m 10H —CH 2 —, 2.8 ppm s 3H NCH 3, 3.9 ppm m 1H —CH—N, 3.9 ppm s 6H OCH 3, 7.1 ppm s 1H CH—O, 7.2 -7.7 ppm 7H aromatic CH)

[Synthesis Example 4]
In a 200 ml two-necked flask, 5.8 g of α-phenyl-2-nitro-4,5-dimethoxybenzyl alcohol, 4.4 g of nitrophenyl chloroformate, and 0.1 g of N, N-dimethyl-4-aminopyridine (DMAP) were added. Then, a mixture of 80 ml of dehydrated N, N-dimethylacetamide and 4.1 g of triethylamine was added dropwise while cooling with ice under a nitrogen stream, and the mixture was stirred for 3 hours. Then, after stirring at room temperature for 2 hours, 1.4 g of nitrophenyl chloroformate was added and stirred overnight. The next day, the reaction solution was put into 1.5 L of ice water, stirred until the ice melted, suction filtered, and the resulting solid was washed with water. Extraction was performed using ethyl acetate, and the organic layer was dehydrated with sodium sulfate and then concentrated with an evaporator to obtain 11.2 g of a yellow solid. By washing with a mixed solvent of hexane and ethyl acetate (volume ratio 1: 1), α-phenyl-2-nitro-4,5-dimethoxybenzyl-4-nitrophenyl carbonate was obtained as a slightly yellowish green solid with HPLC purity of 97 0.7 area%, isolated yield 50%.
α-phenyl-2-nitro-4,5-dimethoxybenzyl-4-nitrophenyl carbonate 4.5 g, 1-hydroxy-7-azabenzotriazole (HOAt) 0.4 g, cis-2,6-dimethylpiperidine 7 g and 50 ml of dehydrated N, N-dimethylacetamide were placed in a 300 ml flask, stirred at 60 ° C. for 3 hours under a nitrogen stream, and then stirred at 70 ° C. for 1 hour. The reaction solution was put into 1.4 L of 1% by weight sodium hydrogen carbonate, and the precipitated solid was subjected to suction filtration. The solid on filtration was washed with 1% by weight of sodium bicarbonate until the filtrate became colorless and transparent, and then washed with water. The obtained solid was transferred to an Erlenmeyer flask, 200 ml of ethyl acetate was added, dehydrated with sodium sulfate, and concentrated with an evaporator. The obtained solid was purified by medium pressure preparative chromatography using a mixed solvent of hexane and ethyl acetate (YFLC-Eprep manufactured by Yamazen Co., Ltd.), and the fraction was concentrated to obtain a solid having a HPLC purity of 97.2 area%. Of 3.6 g was obtained. This was further recrystallized using a mixed solvent of ethanol and hexane (volume ratio 1: 8), and N- (α-phenyl-2-nitro-4,5-dimethoxybenzyl represented by the following formula of slightly yellow crystals. 3.1 g of oxycarbonyl) -2,6-dimethylpiperidine (photobase generator 4) was obtained. The HPLC purity was 98.5 area%, and the isolated yield based on α-phenyl-2-nitro-4,5-dimethoxybenzyl alcohol was 36%. This compound was identified by ¹ H-NMR (1.0 ppm d 3H —CH ₃ , 1.3 ppm d 3H —CH ₃ , 1.4-1.9 ppm m 6H —CH ₂ —, 3.9 ppm s 6H OCH ₃ 3.9 ppm s 6H OCH ₃ , 4.4 ppm m 2H —CH—N, 7.1 ppm s 1H CH—O, 7.2-7.7 ppm 7H aromatic C—H).

[Synthesis Example 5]
Synthetic Example 4 except that α- (4-nitrophenyl) -2-nitro-4,5-dimethoxybenzyl alcohol was used instead of α-phenyl-2-nitro-4,5-dimethoxybenzyl alcohol By the same operation, N- (α- (4-nitrophenyl) -2-nitro-4,5-dimethoxybenzyloxycarbonyl) -2,6-dimethylpiperidine represented by the following formula (photobase generator 5) Was synthesized (isolation yield 33%). This compound was identified by ^{1 H-NMR (1.1ppm d 3H} -CH 3, 1.3ppm d 3H -CH 3, 1.4-1.9ppm m 6H -CH 2 -, 3.9ppm s 3H OCH 3 3.9 ppm s 3H OCH ₃ , 4.4 ppm m 2H —CH—N, 7.1 ppm s 1H CH—O, 7.5-8.2 ppm 6H aromatic C—H).

[Synthesis Example 6]
Except for using α- (2-nitro-4,5-dimethoxyphenyl) -2-nitro-4,5-dimethoxybenzyl alcohol instead of using α-phenyl-2-nitro-4,5-dimethoxybenzyl alcohol In the same manner as in Synthesis Example 4, N- (α- (2-nitro-4,5-dimethoxyphenyl) -2-nitro-4,5-dimethoxybenzyloxycarbonyl) -2 represented by the following formula: 6-dimethylpiperidine (photobase generator 6) was synthesized (isolation yield 16%). This compound was identified by ¹ H-NMR (1.3 ppm d 6H —CH ₃ , 1.4-1.9 ppm m 6H —CH ₂ —, 3.7 ppm s 6H OCH ₃ , 4.0 ppm s 6H OCH ₃ , 4.3 ppm m 2H —CH—N, 6.7 ppm s 2H aromatic C—H, 7.7 ppm s 2H aromatic C—H, 7.9 ppm s 1H CH—O).

[Synthesis Example 7]
N- (α-phenyl-2-nitro-4,5-dimethoxybenzyl represented by the following formula was obtained in the same manner as in Synthesis Example 4 except that piperidine was used instead of cis-2,6-dimethylpiperidine. Oxycarbonyl) piperidine (photobase generator 7) was synthesized (isolation yield 16%). This compound was identified by ¹ H-NMR (1.4-1.8 ppm m 6H —CH ₂ —, 3.5 ppm br 4H —CH ₂ —N, 3.9 ppm s 3H OCH ₃ , 3.9 ppm s 3H OCH ₃ , 7.0 ppm s 1H CH—O, 7.2-7.7 ppm 7H aromatic C—H).

[Comparative Synthesis Example 1]
9.53 g of 2-nitro-4,5-dimethoxybenzyloxycarbonylcyclohexyl from 6.24 g of 2-nitro-4,5-dimethoxybenzyl alcohol and 5.13 g of cyclohexyl isocyanate with reference to JP-A-6-345711 An amine (Comparative Photobase Generator 1) was obtained.

[Comparative Synthesis Example 2]
Under a nitrogen atmosphere, 8.2 g of 4,5-dimethoxy-2-nitrobenzaldehyde was dissolved in 100 mL of dehydrated 2-propanol in a 200 mL three-necked flask equipped with a Dean-Stark apparatus, and 2.0 g of aluminum isopropoxide was added to the mixture at 105 ° C. And stirred for 7 hours. Along with the decrease in solvent evaporation, 40 mL of 2-propanol was added four times. After stopping the reaction with 150 mL of 0.2N hydrochloric acid, extraction was performed with chloroform, and the solvent was distilled off under reduced pressure to obtain 7.2 g of 6-nitroveratryl alcohol.
Under a nitrogen atmosphere, 5.3 g of 6-nitroveratryl alcohol was dissolved in 100 mL of dehydrated dimethylacetamide in a 200 mL three-necked flask, and 7.0 mL of triethylamine was added. In an ice bath, 5.5 g of p-nitrophenyl chloroformate was added, and the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into 2 L of water, and the resulting precipitate was filtered and purified by silica gel column chromatography to obtain 6.4 g of 4,5-dimethoxy-2-nitrobenzyl-p-nitrophenyl carbonate. .
Under a nitrogen atmosphere, 3.6 g of 4,5-dimethoxy-2-nitrobenzyl-p-nitrophenyl carbonate was dissolved in 50 mL of dehydrated dimethylacetamide in a 100 mL three-necked flask, 5 mL of 2,6-dimethylpiperidine, 1-hydroxybenzo 0.36 g of triazole was added and the mixture was stirred with heating at 90 ° C. for 18 hours. The reaction solution was poured into 1 L of a 1% aqueous sodium hydrogen carbonate solution, the resulting precipitate was filtered, and then washed with water, whereby N-{[(4,5- Dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine (2.7 g, comparative photobase generator 2) was obtained.

[Synthesis Example 3: Synthesis of polyimide precursor]
In a 500 mL four-necked separable flask purged with nitrogen, 20.0 g (100 mmol) of 4,4′-diaminodiphenyl ether and 200 mL of dehydrated N-methylpyrrolidone were added and dissolved by stirring in an ice bath. To this solution, 29.4 g (100 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and stirred for 2 hours in an ice bath. The reaction solution was reprecipitated with acetone, and the precipitate obtained by filtration was dried under reduced pressure at room temperature for 8 hours, whereby polyamic acid (polyimide precursor 1) was quantitatively obtained as a white solid.

<Test>
(1) Measurement of molar extinction coefficient Photobase generators 1 to 7 and comparative photobase generators 1 and 2 are weighed using an electronic balance, respectively, and a concentration of 10 ⁻⁴ mol / L is obtained using a measuring flask. Acetonitrile solution was prepared. This solution was put in a quartz cell (optical path length: 1 cm), and an ultraviolet-visible absorption spectrum in a wavelength range of 190 to 800 nm was measured with a spectrophotometer (Shimadzu Corporation UV-2550). From the absorbance obtained from the spectrum, the molar extinction coefficient ε (365, 405, 436 nm) was measured by the following formula. The results are shown in Table 1. It was found that the photobase generators 1 to 6 used in the present invention absorb light having wavelengths of 405 and 436 nm. It was found that the photobase generator 7 absorbs light having a wavelength of 405 nm. The comparative photobase generators 1 and 2 did not absorb at a wavelength of 436 nm, and the absorption was weaker than that of the photobase generators 1 to 7 even at 405 nm.

(2) Measurement of optical resolution About photobase generators 1-7 and comparative photobase generators 1-2, 1.0 mg was weighed into an quartz NMR tube using an electronic balance, and 0.5 mL of heavy acetonitrile was added. Dissolved. Through this filter, all the wavelengths of a high-pressure mercury lamp (SPOT CURE SP-III 250UA, lamp model number: USH-255BY, manufactured by USHIO INC.) Are passed through the filter 1 that does not transmit a wavelength of 350 nm or less before passing through the filter at 100 J / cm ² (i Line conversion: UV illuminance meter: UIT-150 manufactured by Ushio Electric Co., Ltd., light receiver: UVD-S365), 18.2 J / cm ² after passing through the filter (i-line conversion: UV illuminance meter: UIT-150 manufactured by Ushio Electric Co., Ltd., light reception) Device: UVD-S365) was irradiated, and the NMR spectra before and after irradiation were compared to evaluate the photodegradability in the wavelength region of i (365 nm) or longer.
Similarly, the total wavelength of the high-pressure mercury lamp is 100 J / cm ² before passing through the filter 2 through the filter 2 that does not transmit the wavelength of 380 nm or less (i-line conversion: ultraviolet illuminance meter: UIT-150 manufactured by Ushio Electric Co., photoreceiver: UVD- S365), 470 J / cm ² (h-line conversion: UV illuminance meter: UIT-101 manufactured by Ushio Electric Co., Ltd., receiver: UVD-405PD), 0 J / cm ² after passing through the filter (i-line conversion: UV illuminance meter: Ushio Electric) Irradiated with before and after irradiation by UIT-150 manufactured by company, light receiver: UVD-S365), 160 J / cm ² (h ray conversion: UV illuminance meter: UIT-101 manufactured by Ushio Electric Co., Ltd., light receiver: UVD-405PD) By comparing the NMR spectra, photodegradability in the wavelength region of h-line (405 nm) or more was evaluated.
FIG. 1 shows transmittance curves of the filter 1 and the filter 2. Table 2 shows the evaluation results of photodegradability.

  It has been clarified that the photobase generators 1 to 7 have photodegradability in the wavelength range of i-line and h-line. Comparative photobase generators 1 and 2 were found to have no photodegradability in h-rays, and i-line sensitivity was inferior to photobase generators 1 to 7.

(3) Measurement of thermal stability About photobase generators 1-7 and comparative photobase generators 1-2, a temperature increase rate of 10 ° C./30° C. to 600 ° C. using DTG-60 (manufactured by Shimadzu Corporation) TG-DTA measurement was performed at min. The 5% weight loss temperature was calculated and the heat resistance was evaluated. Table 3 shows the evaluation results of heat resistance.

  Photobase generators 1-7 and comparative photobase generators 1-2 were found to have a 5% weight loss temperature of 200 ° C. or higher.

Example 1
The photobase generator 1 was dissolved in 0.2 g, the polyimide precursor 1 was dissolved in 1 g, and N-methylpyrrolidone 9 g to obtain a photosensitive resin composition (photosensitive resin composition 1) of the present invention.

(Example 2)
0.18 g of the photobase generator 1, 1.2 g of the polyimide precursor 1 and 8.8 g of N-methylpyrrolidone were dissolved to obtain a photosensitive resin composition (photosensitive resin composition 2) of the present invention. .

(Example 3)
The photobase generator 3 was dissolved in 0.18 g, the polyimide precursor 1 was dissolved in 1.2 g, and N-methylpyrrolidone 8.8 g to obtain a photosensitive resin composition (photosensitive resin composition 3) of the present invention. .

(Comparative Example 1)
Comparative photobase generator 1 was dissolved in 0.18 g, the polyimide precursor 1 was dissolved in 1.2 g, and N-methylpyrrolidone 8.8 g to obtain a photosensitive resin composition (comparative photosensitive resin composition 1).

(Comparative Example 2)
Comparative photobase generator 2 was dissolved in 0.18 g, the polyimide precursor 1 was dissolved in 1.2 g and N-methylpyrrolidone 8.8 g to obtain a photosensitive resin composition (comparative photosensitive resin composition 2).

[Evaluation]
(1) Thermosetting temperature Using photosensitive resin composition 1, a coating film that was exposed to generate amine from the photobase generator, and a coating film that was not exposed to light and did not generate amine from the photobase generator The difference of the imidation ratio of the polyimide precursor by presence or absence of amine was observed.
The photosensitive resin composition 1 was spin-coated on a chromium-plated glass plate so as to have a final film thickness of 1 μm, and dried on a hot plate at 100 ° C. for 5 minutes. Thereto, 2J / cm ² ultraviolet-visible light irradiation was performed in terms of i-line with a manual exposure apparatus (manufactured by Dainippon Kaken, MA-1100). The infrared spectroscopic spectrum of this coating film and the unexposed coating film was measured using a Varian FTS7000 and an AS ONE HOTPLATE EC-1200 while heating from room temperature to 5 ° C./min to 300 ° C.
The spectrum derived from the precursor disappeared with heating, and a peak derived from polyimide generated by heating appeared. In order to confirm the progress of imidization, the peak height of 1770 cm ⁻¹ derived from the produced polyimide after measurement was plotted.

  The result is as shown in FIG. In the coating film that was exposed to light and generated amine from the photobase generator, the precursor decreased at a lower temperature than the coating film that did not generate amine from the unexposed photobase generator. It was found that the difference in the imidization ratio depending on the presence or absence was the maximum at around 170 ° C. It was found that the PEB temperature is preferably 140 ° C. to 200 ° C. from the difference in the imidization ratio between the exposed and unexposed areas.

(2) Pattern formation The photosensitive resin composition 2 was spin-coated on a glass plate so as to have a film thickness of 10 μm after drying, and dried on a hot plate at 100 ° C. for 15 minutes. Then, after performing ultraviolet-visible light irradiation of 3000 mJ / cm ^{2 in} terms of i-line with a manual exposure device (manufactured by Dainippon Kaken, MA-1100), and then heating on a hot plate at 145 ° C. for 10 minutes, Tetramethylammonium hydroxide was immersed in a solution obtained by adding 10 wt% of isopropanol to a 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.

Similarly, pattern formation was performed using the photosensitive resin composition 3, and a pattern was obtained in which the exposed portion was not dissolved in the developer during 3000 mJ / cm ² exposure.

Similarly, pattern formation was performed using the comparative photosensitive resin composition 1, but even at the time of exposure to 6000 mJ / cm ² , the remaining film ratio in the exposed portion was lowered and a good pattern film could not be obtained. It was.

Similarly, pattern formation was performed using the comparative photosensitive resin composition 2, but even when exposed to 6000 mJ / cm ² , the remaining film ratio in the exposed portion was lowered, and a good pattern film could not be obtained. It was.

Claims (15)

The photosensitive resin composition containing the photobase generator represented by general formula (I), and a polyimide precursor.

(In the above general formula (I), R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms. R ₁ and R ₂ are linked to form an alkylene group having 1 to 24 carbon atoms which may have a substituent or an arylene group having 6 to 24 carbon atoms which may have a substituent. You can,
R ₃ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms, and R ₃ And at least one of R ₄ is not a hydrogen atom, but R ₃ and R ₄ may be linked to form a cyclic structure that may contain a hetero atom,
R _{5 to} R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, or a carbon number. An alkylamino group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a nitro group, or an acyl group having 1 to 12 carbon atoms; ) 2. The photosensitive resin composition according to claim 1, wherein in the photobase generator, R ₃ and R ₄ are a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent. In the photobase generator, R ₃ and R ₄ is an alkyl group having 1 to 12 carbon atoms which may have a substituent group, claim 1, wherein or a photosensitive resin composition according to paragraph 2 . The photosensitive resin composition according to claim 1, wherein in the photobase generator, R ₃ and R ₄ are linked to form a cyclic structure that may contain a hetero atom. The photosensitive resin composition in any one of Claim 1 thru | or 4 whose R < ₁ > and R < ₂ > is a methyl group in the photobase generator represented by the said general formula (I).   The photosensitive resin composition according to any one of claims 1 to 5, wherein the polyimide precursor itself is one whose reaction to the final product is promoted by the action of a basic substance. .   The polyimide precursor according to any one of claims 1 to 6, wherein the polyimide precursor itself is a substance whose reaction to the final product is promoted by the action of a basic substance and whose solubility is changed by heating. A photosensitive resin composition according to claim 1.   Furthermore, the photosensitive resin composition in any one of the Claims 1 thru | or 7 containing a sensitizer.   The photosensitive resin composition in any one of Claim 1 thru | or 8 whose said polyimide precursor is a polyamic acid.   The photosensitive resin composition in any one of Claim 1 thru | or 9 with which the said photobase generator has photodegradability with respect to the electromagnetic waves with a wavelength of 400 nm or more.   The photosensitive resin composition in any one of Claim 1 thru | or 10 whose 5% weight reduction | decrease temperature of the said photobase generator is 170 degreeC or more.   Paint or printing ink, or color filter, flexible display film, semiconductor device, electronic component, interlayer insulation film, wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material The photosensitive resin composition according to any one of claims 1 to 11, which is used as a material.   A printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, at least partly formed of the photosensitive resin composition according to any one of claims 1 to 12 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 body comprising the photosensitive resin composition according to any one of claims 1 to 12 is irradiated with electromagnetic waves in a predetermined pattern, and the coating film or molded body A negative pattern forming method of developing after selectively reducing the solubility of an electromagnetic wave irradiation site.   The negative pattern forming method according to claim 14, wherein the heat treatment is performed after the irradiation with the electromagnetic wave to selectively reduce the solubility of the electromagnetic wave irradiation site of the coating film or molded body.

Images