JP2012211276A - Base generator, photosensitive resin composition, pattern-forming material comprising the photosensitive resin composition, method of producing relief pattern by using the photosensitive resin composition, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-cost photosensitive resin composition having high-resolution and having a wide range of choices constitutionally applicable to a macromolecular precursor whose reaction to a final product is promoted by a basic substance or by heating in the presence of the basic substance, and to provide a base generator that can be used for such photosensitive resin composition.SOLUTION: This invention relates to the photosensitive resin composition, comprising: the base generator that has a specific structure and generates a base by the irradiation of electromagnetic wave and the heating; and the macromolecular precursor whose reaction to the final product is promoted by the base generator and the basic substance or by heating in the presence of the basic substance.

Description

  The present invention relates to a base generator that generates a base upon irradiation and heating of electromagnetic waves, and a photosensitive resin composition using the base generator, and in particular, a product formed through a patterning step or a curing acceleration step using electromagnetic waves. Or the photosensitive resin composition which can be utilized suitably as a material of a member, the pattern formation material which consists of the said photosensitive resin composition, the manufacturing method of a relief pattern, and the articles | goods produced using the said resin composition Is.

The photosensitive resin composition is used for, for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material or an adhesive, and particularly preferably used for a product or a member formed through a patterning process using electromagnetic waves. Has been.
For example, polyimide, which is a polymer material, exhibits top-class performance among organic materials such as heat resistance, dimensional stability, and insulation characteristics, so it is widely applied to insulating materials for electronic components. It has been actively used as a coating film, a base material for flexible printed wiring boards, and the like.
In recent years, in order to solve the problems of polyimide, there are polybenzoxazole, which has low water absorption and low dielectric constant, and polybenzimidazole with excellent adhesion to the substrate, to which processing processes similar to polyimide are applied. It has been studied energetically.

  In general, polyimide is poorly soluble in a solvent and difficult to process. As a method for patterning polyimide into a desired shape, patterning is performed by exposure and development in the state of a polyimide precursor having excellent solvent solubility, and then heat treatment. For example, there is a method of obtaining a polyimide pattern by imidization by the method described above.

Various methods have been proposed as means for forming a pattern using a polyimide precursor. Two typical ones are as follows.
(1) A method of forming a pattern by providing a photosensitive resin as a resist layer on a polyimide precursor without a pattern forming ability in a polyimide precursor (2) Bonding or coordination of a photosensitive site to the polyimide precursor itself A method of forming a pattern by its action. Alternatively, a method in which a photosensitive component is mixed with a polyimide precursor to form a resin composition, and a pattern is formed by the action of the photosensitive component.

  As a typical patterning technique using the above (2), (i) a polyimide precursor polyamic acid acts as a dissolution inhibitor before exposure to electromagnetic waves, and after exposure, a carboxylic acid is formed to form a dissolution accelerator; The naphthoquinonediazide derivative is mixed, and pattern formation is performed by increasing the contrast of the dissolution rate of the exposed area and unexposed area to the developer, followed by imidization to obtain a polyimide pattern (Patent Document 1) (Ii) A methacryloyl group is introduced into the polyimide precursor via an ester bond or an ionic bond, a photo radical generator is added thereto, and the exposed area is crosslinked to dissolve the exposed and unexposed areas in the developer. A method to obtain a polyimide pattern by forming a pattern by increasing the speed contrast and then imidizing it Etc. have been put into practical use (Patent Document 2).

  Compared with the method (1), the method (2) does not require a resist layer and can greatly simplify the process. However, in the method (i), a naphthoquinonediazide derivative is used to increase the solubility contrast. When the amount of addition is increased, there is a problem that the original physical properties of the polyimide cannot be obtained. Further, the method (ii) has a problem that the structure of the polyimide precursor is restricted.

  As another patterning technique, (iii) a polyamic acid as a polyimide precursor is mixed with a photobase generator and heated after exposure to cause cyclization to proceed by the action of a base generated by exposure. A technique for obtaining a polyimide pattern by reducing the solubility, forming a pattern by increasing the contrast of the dissolution rate in the developing solution of the exposed part and the unexposed part, and then imidizing is reported ( Patent Document 3).

  As another example of the photosensitive resin composition using the photobase generator, there is an example using an epoxy compound (for example, Patent Document 4). By irradiating the photobase generator with light, amines are generated in the layer containing the epoxy compound, so that the amines act as an initiator or a catalyst, and the epoxy compound can be cured only in the exposed area. Pattern formation can be performed.

  Non-Patent Document 1 discloses the use of o-hydroxy-trans-cinnamic acid as a photoreactive protecting group for amines. Patent Document 5 discloses a photosensitive resin composition containing o-hydroxy-trans-cinnamic acid amide as a photobase generator and containing the photobase generator and a base-reactive resin. Furthermore, the present inventors also patented a photosensitive resin composition containing an o-hydroxy-trans-cinnamic acid amide derivative as a photocyclization type photobase generator and containing the photobase generator and a polymer precursor. This is disclosed in Document 6 and Patent Document 7. Since these photobase generators are excellent in high temperature resistance, it is possible to form a pattern without generating a base in an unexposed portion by heating.

JP 52-13315 A JP 54-145794 A JP-A-8-227154 Japanese Patent Laid-Open No. 2003-212856 JP 2009-80452 A International Publication No. 2009/123122 Pamphlet JP 2010-254946 A

Chem. Pharm. Bull. 1997, 45 (4) p.715-718

  A photosensitive resin composition using a photobase generator is a resin composition because a photosensitive polymer precursor can be obtained simply by mixing a photobase generator at a certain ratio with an existing polymer precursor. The process for manufacturing is simple. In particular, a polyimide precursor in which the structure of a precursor compound used in the past is restricted has an advantage of high versatility because it can be applied to polyimide precursors having various structures. However, as shown in a comparative example described later, the conventional photobase generator has a problem that the irradiation amount of electromagnetic waves increases because the sensitivity is still insufficient. When the amount of electromagnetic wave irradiation increases, there is also a problem that the processing amount (throughput) per unit time decreases. In order to improve the throughput (throughput) per unit time, further enhancement of sensitivity has been desired.

  Further, even when the conventional photobase generator is purified by reprecipitation or crystallization, the hydrophobicity and crystallinity are low, so there is a problem that the purity tends to deteriorate and the yield is low.

  The present invention has been made in view of the above circumstances, and its main purpose is high sensitivity, easy purification, and a base generator that can be used regardless of the type of polymer precursor, and excellent sensitivity. Regardless of the type of polymer precursor, a high solubility contrast is obtained between the exposed and unexposed areas, resulting in a photosensitivity capable of obtaining a pattern with a good shape while maintaining a sufficient process margin. The object is to provide a resin composition.

  The base generator according to the present invention is represented by the following chemical formula (1) and is characterized by generating a base by irradiation with electromagnetic waves and heating.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は有機基であり、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^１及びＲ^２の少なくとも１つは有機基である。Ｒ^３及びＲ^４はそれぞれ独立に、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基であり、同一であっても異なっていても良い。Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基であり、同一であっても異なっていても良く、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８のいずれかは、置換基を有してもよいシクロアルコキシ基又は３級アルコキシ基を有する。Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それらの２つ以上が結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。Ｒ^９は、水素原子、或いは、加熱及び／又は電磁波の照射により脱保護可能な保護基である。）

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R ¹ and R ² is an organic group, and R ³ and R ⁴ are each independently hydrogen, halogen, Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, which are the same be different even good ^{.R 5, R 6,} R ⁷ and ^{R 8} are each independently hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, two Nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group, may be different even in the same, R ^5, R ⁶ , any one of R ⁷ and R ⁸ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are two or more of them. It may be bonded to form a cyclic structure and may contain a heteroatom bond, and R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves. )

Since the base generator represented by the chemical formula (1) has the above specific structure, it generates a basic substance with a small amount of electromagnetic wave irradiation by combining electromagnetic wave irradiation and heating. It is an excellent base generator that can be used regardless of the type of polymer precursor and is highly versatile.
In particular, the base generator represented by the chemical formula (1) has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent as a substituent of the aromatic ring. A cycloalkoxy group or a tertiary alkoxy group is presumed to be a functional group having a stronger electron donating property than a primary alkoxy group such as a methoxy group or a chain-like secondary alkoxy group. When the base generator represented by the chemical formula (1) is substituted with a cycloalkoxy group or a tertiary alkoxy group, the electron donating property to the aromatic ring is strengthened, and the electron density of the aromatic ring, which is a photophore, is improved. Therefore, it is estimated that a basic substance can be generated with a small amount of electromagnetic wave irradiation and high sensitivity can be achieved. In addition to improving the sensitivity of the compound alone, the sensitivity of the coating film is improved by introducing a bulky substituent such as a cyclic alkoxy group or a tertiary alkoxy group as a substituent. It is presumed that a fine space was created inside, and the generated base was easily diffused to improve the sensitivity.
Furthermore, the base generator represented by the chemical formula (1) is a compound that improves the hydrophobicity of the compound by introducing a cyclic alkoxy group or a tertiary alkoxy group, and is easily purified by a reprecipitation method or the like. . Therefore, the base generator represented by the chemical formula (1) tends to have high purity and high yield in production. In particular, in the case of having a cyclic alkoxy group or a tertiary alkoxy group having a small number of carbon atoms in a straight-chain hydrocarbon, purification becomes easier by crystallization, and a compound with high purity can be obtained in a high yield.

  In addition, the photosensitive resin composition according to the present invention relates to a polymer precursor whose reaction to the final product is accelerated by heating with a basic substance or in the presence of the basic substance, and the above-described present invention. It contains a base generator.

  The photosensitive resin composition according to the present invention is represented by the chemical formula (1) and generates a base upon irradiation with electromagnetic waves and heating, with a basic substance or by heating in the presence of a basic substance. By combining with a polymer precursor that promotes reaction to the final product, high sensitivity, regardless of the type of polymer precursor, a large solubility contrast can be obtained between exposed and unexposed areas, As a result, it is possible to obtain a pattern having a good shape while maintaining a sufficient process margin.

In the present invention, in the base generator represented by the chemical formula (1), R ⁶ and / or R ⁷ may have a cycloalkoxy group and / or a tertiary alkoxy group which may have a substituent. This is preferable from the viewpoint of high sensitivity.

  In the base generator of the present invention, the cycloalkoxy group is a monocyclic or polycyclic cycloalkoxy group containing a 5-membered ring, a 6-membered ring, and / or a 7-membered ring. It is preferable from the point.

  In the base generator of the present invention, the cycloalkoxy group preferably has 5 to 20 carbon atoms from the viewpoint of increasing sensitivity.

  In the base generator of the present invention, the tertiary alkoxy group preferably has 4 to 20 carbon atoms from the viewpoint of increasing sensitivity.

  In the photosensitive resin composition according to the present invention, the polymer precursor includes a compound and polymer having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzo. One or more selected from the group consisting of oxazole precursors is preferably used.

  In the photosensitive resin composition according to the present invention, the polymer precursor is preferably soluble in a basic solution from the viewpoint that the solubility contrast between the exposed portion and the unexposed portion can be increased.

  In one embodiment of the present invention, a polyimide precursor such as polyamic acid or a polybenzoxazole precursor can be used as the polymer precursor of the photosensitive resin composition. When such a polymer precursor is used, a photosensitive resin composition having excellent physical properties such as heat resistance, dimensional stability, and insulating properties can be obtained. The polyimide precursor is preferably a polyamic acid from the viewpoint of easy availability of raw materials.

Moreover, this invention provides the material for pattern formation which consists of the photosensitive resin composition which concerns on the said invention.
Furthermore, this invention provides the manufacturing method of the relief pattern using the said photosensitive resin composition.
The method for producing a relief pattern according to the present invention comprises forming a coating film or a molded body using the photosensitive resin composition, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, and after irradiation or irradiation. It develops, after heating simultaneously and changing the solubility of the said irradiation part, It is characterized by the above-mentioned.
In the method for producing a relief pattern, a coating film or a molding made of a photosensitive resin composition is used by combining a polymer precursor and a compound represented by the chemical formula (1) as a base generator. Pattern formation for development can be performed without using a resist film for protecting the surface of the body from the developer.

  The present invention also provides a printed material, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, light, which is at least partly formed of the photosensitive resin composition or a cured product thereof. Articles of either shaped objects, optical members or building materials are also provided.

Since the base generator of the present invention has the above-mentioned specific structure, purification is easy, it can be used regardless of the type of the polymer precursor, and high sensitivity can be achieved.
In the photosensitive resin composition of the present invention, since the base generator represented by the chemical formula (1) contained has superior sensitivity compared to a conventionally used photobase generator, the photosensitive resin is highly sensitive. It is a composition. Furthermore, in the photosensitive resin composition of the present invention, unlike an acid, a base does not cause metal corrosion, so that a more reliable cured film can be obtained.
In addition, when the pattern forming step includes a heating step, the photosensitive resin composition of the present invention can use the heating step in heating that promotes the generation of a base. , It has the advantage that the irradiation amount of electromagnetic waves can be reduced. Therefore, when used in a process including such a heating process, the photosensitive resin composition of the present invention can be streamlined compared to a conventional resin composition that generates a base only by electromagnetic wave irradiation.

FIG. 1 is a graph showing the relationship between the exposure amount and the remaining film ratio, which was prepared using the photosensitive resin composition (1) and the comparative photosensitive resin composition (1).

The present invention will be described in detail below.
In the present invention, the cycloalkoxy group means a group in which an alicyclic hydrocarbon group is bonded to an oxygen atom among the alkoxy groups, and the tertiary alkoxy group is directly bonded to an oxygen atom in the alkoxy group. The group in which the carbon atom is a tertiary carbon atom bonded to the other three carbon atoms.
In the present invention, (meth) acryloyl means acryloyl and / or methacryloyl, (meth) acryl means acryl and / or methacryl, and (meth) acrylate means acrylate and / or methacrylate. Means.
In the present invention, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam, unless the wavelength is specified. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure. Note that electromagnetic waves with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.
<Base generator>
The base generator according to the present invention is represented by the following chemical formula (1) and is characterized by generating a base by irradiation with electromagnetic waves and heating.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は有機基であり、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^１及びＲ^２の少なくとも１つは有機基である。Ｒ^３及びＲ^４はそれぞれ独立に、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基であり、同一であっても異なっていても良い。Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基であり、同一であっても異なっていても良く、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８のいずれかは、置換基を有してもよいシクロアルコキシ基又は３級アルコキシ基を有する。Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それらの２つ以上が結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。Ｒ^９は、水素原子、或いは、加熱及び／又は電磁波の照射により脱保護可能な保護基である。）

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R ¹ and R ² is an organic group, and R ³ and R ⁴ are each independently hydrogen, halogen, Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, which are the same be different even good ^{.R 5, R 6,} R ⁷ and ^{R 8} are each independently hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, two Nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group, may be different even in the same, R ^5, R ⁶ , any one of R ⁷ and R ⁸ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are two or more of them. It may be bonded to form a cyclic structure and may contain a heteroatom bond, and R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves. )

The base generator of the present invention is a kind of photobase generator and generates a base only by being irradiated with electromagnetic waves. However, generation of a base is promoted by appropriate heating. Since the base generator of the present invention has the above specific structure, it is possible to efficiently generate a base with a small amount of electromagnetic wave irradiation by combining electromagnetic wave irradiation and heating. Excellent sensitivity compared to the agent. In particular, since the base generator represented by the chemical formula (1) has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent as a substituent of the aromatic ring, o-hydroxy High sensitivity can be achieved among trans-cinnamic amide derivatives. In the cycloalkoxy group, the carbon atom directly bonded to the oxygen atom is a secondary carbon atom and is cyclic, and in the tertiary alkoxy group, the carbon atom directly bonded to the oxygen atom is a tertiary carbon atom. Compared with primary alkoxy groups such as methoxy groups and chain-like secondary alkoxy groups, it is presumed to be a functional group having a strong electron donating property. When the base generator represented by the chemical formula (1) is substituted with a cycloalkoxy group or a tertiary alkoxy group, the electron donating property to the aromatic ring is strengthened, and the electron density of the aromatic ring, which is a photophore, is improved. Therefore, it is estimated that a basic substance can be generated with a small amount of electromagnetic wave irradiation and high sensitivity can be achieved. In addition to improving the sensitivity of the compound alone, the sensitivity of the coating film is improved by introducing a bulky substituent such as a cyclic alkoxy group or a tertiary alkoxy group as a substituent. It is presumed that a fine space was created inside, and the generated base was easily diffused to improve the sensitivity.
Furthermore, the base generator represented by the chemical formula (1) is a compound that improves the hydrophobicity of the compound by introducing a cyclic alkoxy group or a tertiary alkoxy group, and is easily purified by a reprecipitation method or the like. . Therefore, the base generator represented by the chemical formula (1) tends to have high purity and high yield in production. In particular, in the case of having a cyclic alkoxy group or a tertiary alkoxy group having a small number of carbon atoms in a straight-chain hydrocarbon, purification becomes easier by crystallization, and a compound with high purity can be obtained in a high yield.
The photobase generator refers to an agent that does not exhibit activity under normal conditions of normal temperature and pressure, but generates a base when electromagnetic waves are applied as an external stimulus.

Since the base generator according to the present invention has the specific structure described above, (-CR ⁴ = CR ³ -C (= O) in the chemical formula (1) as shown by the following formula when irradiated with electromagnetic waves. The)-) moiety isomerizes to the cis isomer and is further cyclized by heating to produce the base (NHR ¹ R ² ). By the catalytic action of the base, the temperature at which the reaction when the polymer precursor becomes the final product can be lowered, or the curing reaction where the polymer precursor becomes the final product can be started.

  When the base generator represented by the chemical formula (1) is cyclized, the phenolic hydroxyl group disappears, the solubility changes, and in the case of a basic aqueous solution, the solubility decreases. Thereby, when the polymer precursor contained in the photosensitive resin composition according to the present invention is a polyimide precursor or a polybenzoxazole precursor, the solubility is further reduced due to the reaction of the precursor to the final product. It has a function of assisting, and it becomes possible to increase the solubility contrast between the exposed portion and the unexposed portion.

R ¹ and R ² are each independently a hydrogen atom or an organic group, but at least one of R ¹ and R ² is an organic group. NHR ¹ R ² is a base (in the present invention, “basic substance” is simply referred to as a base), but R ¹ and R ² are each an organic group that does not contain an amino group. Is preferred. If an amino group is contained in R ¹ and R ² , the base generator itself becomes a basic substance, which accelerates the reaction of the polymer precursor, resulting in a solubility contrast between the exposed and unexposed areas. There is a risk of the difference becoming smaller. However, when there is a difference in basicity between the electromagnetic wave irradiation and the base generated after heating, such as when an amino group is bonded to the aromatic ring present in the organic group of R ¹ and R ^2. May be used even if the organic group of R ¹ and R ² contains an amino group.
Examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.
The organic group in R ¹ and R ² is usually a monovalent organic group, but in the case of forming a cyclic structure described later, the generated NHR ¹ R ² is an NH group capable of forming an amide bond such as diamine. In the case of a basic substance having two or more, it can be a divalent or higher organic group.

R ¹ and R ² may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond. , Amide bond, urethane bond, imino bond (—N═C (—R) —, —C (═NR) —, where R is a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, sulfinyl bond And an azo bond.
From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (— R)-, -C (= NR)-: R is preferably a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, or sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired. A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group Acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and Arylthioether group, a Amino group (-NH2, -NHR, -NRR ': wherein, R and R' are independently a hydrocarbon group) include an ammonio group. The hydrogen contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
Examples of the substituent other than the hydrocarbon group in the organic group of R ¹ and R ² include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, Silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group , A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group.

Since the base to be generated is NHR ¹ R ² , primary amines, secondary amines, or heterocyclic compounds can be mentioned. The amine includes an aliphatic amine and an aromatic amine, respectively. In addition, the heterocyclic compound here means that NHR ¹ R ² has a cyclic structure and has aromaticity. Non-aromatic heterocyclic compounds that are not aromatic heterocyclic compounds are included here in aliphatic amines as alicyclic amines.

Further, the NHR ¹ R ^{2 to be} generated is not only a base such as monoamine having only one NH group capable of forming an amide bond, but also two or more NH groups capable of forming an amide bond such as diamine, triamine, and tetraamine. It may be a base. In the case where the generated NHR ¹ R ² is a base having two or more NH groups, an NH group capable of forming an amide bond is formed at one or more terminals of R ¹ and / or R ^{2 in} the chemical formula (1). The structure which the photolatent part which generate | occur | produces the base which has by irradiation of electromagnetic waves and a heating has couple | bonded further is mentioned. As the photolatent site, to one or more ends of the R ¹ and / or R ² of Formula (1), residues obtained by removing R ¹ and / or R ² is further bonded of formula (1) Structure.

Among the generated NHR ¹ R ² , aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, isoamylamine, tert-pentylamine. , Cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, cycloheptaneamine, octylamine, 2-octaneamine, 2,4,4-trimethylpentan-2-amine, cyclooctylamine and the like.

  Examples of the aromatic primary amine include aniline, 2-aminophenol, 3-aminophenol, and 4-aminophenol.

  Aliphatic secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, methylaziridine, dimethylaziridine, methylazetidine, dimethyl Examples thereof include azetidine, trimethylazetidine, methylpyrrolidine, dimethylpyrrolidine, trimethylpyrrolidine, tetramethylpyrrolidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine and the like, among which alicyclic amine is preferable.

  Aromatic secondary amines include methylaniline, diphenylamine, and N-phenyl-1-naphthylamine. In addition, as an aromatic heterocyclic compound having an NH group capable of forming an amide bond, an imino bond (—N═C (—R) —, —C (═NR) — Here, R preferably has a hydrogen atom or a monovalent organic group), and examples thereof include imidazole, purine, triazole, and derivatives thereof.

Bases having two or more NH groups capable of forming an amide bond include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7- Linear aliphatic alkylenediamines such as heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1 , 4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1 Branched aliphatic alkylenediamines such as 1,4-butanediamine and 2,3-dimethyl-1,4-butanediamine; diethylenetriamine, triethylenetetra Emissions, polyethylene amines represented by the general formula _{NH 2 (CH 2 CH 2 NH} ) n H , such as tetraethylene pentamine; cyclohexane diamine, methylcyclohexane diamine, isophorone diamine, norbornane dimethylamine, tricyclodecane dimethylamine, noodles Alicyclic diamines such as diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, diaminodiphenylsulfone; benzenetriamine, Examples thereof include triamines such as melamine and 2,4,6-triaminopyrimidine; tetraamines such as 2,4,5,6-tetraaminopyrimidine.

Depending on the substituents introduced at the positions of R ¹ and R ² , the thermal properties and basicity of the generated base are different.
Catalytic action, such as lowering the reaction start temperature for the reaction from the polymer precursor to the final product, is more effective as a catalyst with a basic material having a higher basicity, and a lower temperature with a smaller amount of addition. Reaction to the final product is possible. In general, secondary amines have higher basicity than primary amines, and their catalytic effect is greater.
In addition, aliphatic amines are preferred over aromatic amines because they are more basic.

  In addition, the base generated in the present invention is preferably a secondary amine and / or a heterocyclic compound, and more preferably a secondary amine, from the viewpoint of increasing sensitivity as a base generator. It is presumed that this is because the use of a secondary amine or a heterocyclic compound eliminates active hydrogen at the amide bond site, thereby changing the electron density and improving the sensitivity of isomerization.

Further, from the viewpoint of the thermophysical properties of the base to be eliminated and the basicity, the organic groups of R ¹ and R ² each independently preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly carbon. It is preferable that it is number 1-8.

In the chemical formula (1), R ³ and R ⁴ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate. Group, phosphino group, phosphinyl group, phosphono group, phosphonato group, or organic group, which may be the same or different. As R ³ and R ⁴ , both are preferably hydrogen from the viewpoint of easily achieving high sensitivity.
On the other hand, in the present invention, particularly when at least one of R ³ and R ^{4 in} the chemical formula (1) is not hydrogen but the specific functional group, both R ³ and R ⁴ are hydrogen. Compared to the case, the base generator of the present invention has further improved solubility in organic solvents and improved affinity with the polymer precursor. For example, when at least one of R ³ and R ⁴ is an organic group such as an alkyl group or an aryl group, the solubility in an organic solvent is improved. For example, when at least one of R ³ and R ⁴ is a halogen such as fluorine, the affinity with a polymer precursor containing a halogen such as fluorine is improved. For example, when at least one of R ³ and R ⁴ has a silyl group or a silanol group, the affinity with the polysiloxane precursor is improved. As described above, R ³ and / or R ⁴ are appropriately combined with a desired organic solvent or polymer precursor to introduce a substituent, thereby improving the solubility in the desired organic solvent or the desired polymer precursor. Affinity with the body is improved.

Examples of the halogen include fluorine, chlorine, bromine and the like.
The organic group is not particularly limited as long as the effect of the present invention is not impaired, and is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. , Cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, etc. Is mentioned. These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched. The organic group in R ³ and R ⁴ is usually a monovalent organic group.
Examples of the bond other than the hydrocarbon group in the organic group of R ³ and R ⁴ and the substituent other than the hydrocarbon group in the organic group include those other than the hydrocarbon group in the organic group mentioned in R ¹ and R ² above. And the same substituents as those other than the hydrocarbon group in the organic group can be used.

Each of R ³ and R ⁴ may be a hydrogen atom, but when it has a substituent, at least one of them is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group or a propyl group; cyclopentyl Group, a cycloalkyl group having 4 to 23 carbon atoms such as a cyclohexyl group; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; a phenoxymethyl group, a 2-phenoxyethyl group, and a 4-phenoxybutyl group An aryloxyalkyl group having 7 to 26 carbon atoms such as -ROAr group; an aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; and a cyano group such as cyanomethyl group and β-cyanoethyl group An alkyl group having 2 to 21 carbon atoms; an alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group, a methoxy group, and ethoxy Carbon such as an alkoxy group having 1 to 20 carbon atoms such as a group, amide group having 2 to 21 carbon atoms such as acetamido group, benzenesulfonamide group (C ₆ H ₅ SO ₂ NH ₂ —), methylthio group, ethylthio group, etc. C1-C20 acyl groups, such as a C1-C20 alkylthio group (-SR group), an acetyl group, a benzoyl group, etc., C2-C21 ester groups, such as a methoxycarbonyl group and an acetoxy group (-COOR group and -OCOR group), a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, etc., an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted by an electron donating group and / or an electron withdrawing group, The electron donating group and / or the electron withdrawing group are preferably a benzyl group, a cyano group, and a methylthio group (—SCH ₃ ) substituted. The alkyl moiety may be linear, branched or cyclic.

In the chemical formula (1), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino. Group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, or organic group, each of which may be the same or different, R ⁵ , R ⁶ , One of R ⁷ and R ⁸ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent. Two or more of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to form a cyclic structure, and may include a hetero atom bond. The organic group in R ^{5 to} R ⁸ is usually a monovalent organic group, but may form a divalent or higher organic group when forming a cyclic structure described later.

The cycloalkoxy group or tertiary alkoxy group which may have the above-described substituent may be included in at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ . Typically, at any position of R ⁵ , R ⁶ , R ⁷ and R ^8, an optionally substituted cycloalkoxy group or tertiary alkoxy group is bonded directly to the benzene ring as a substituent. Structure. When two or more of R ^{5 to} R ⁸ are bonded and share a benzene ring atom to which they are bonded to form a condensed ring such as naphthalene, anthracene, phenanthrene, indene, fluorene, etc. The structure may have a cycloalkoxy group or a tertiary alkoxy group which may have a substituent as a substituent.

  The cycloalkoxy group is preferably a cycloalkoxy group having 5 to 20 carbon atoms, more preferably a cycloalkoxy group having 5 to 15 carbon atoms, from the viewpoint of increasing sensitivity. A cycloalkoxy group having a number of 5 to 10 is more preferable in terms of easy availability and ease of purification. The cycloalkoxy group is a monocyclic or polycyclic cycloalkoxy group containing a 5-membered ring, a 6-membered ring, and / or a 7-membered ring. It is preferable from the point.

  Examples of the cycloalkoxy group include monocyclic hydrocarbons such as a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclononyloxy group, a cyclohexenyloxy group, and a cyclooctadienyloxy group. Group, 1-adamantyloxy group, 2-adamantyloxy group, 1-norbornyloxy group, bicyclo [4.3.0] nonanyloxy group, decahydronaphthalenyloxy group, tricyclo [5.2.1 .0 (2,6)] decanyloxy group, bornyloxy group, isobornyloxy group, noradamantyloxy group, 1,7,7-trimethyltricyclo [2.2.1.0 (2,6)] heptanyloxy group , 3,7,7-trimethylbicyclo [4.1.0] heptanyloxy group, etc. It can be exemplified hydrogen group.

The cycloalkoxy group may have a substituent, and examples of the substituent include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated alkyl halide. Group, halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group Nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, saturated or unsaturated alkyl Ether group, saturated or Examples include unsaturated alkyl thioether groups, aryl ether groups, and aryl thioether groups, amino groups (-NH2, -NHR, -NRR ': where R and R' are each independently a hydrocarbon group), ammonio groups, and the like. .
Preferably saturated or unsaturated alkyl group, saturated or unsaturated cycloalkyl group, aryl group, aralkyl group, and saturated or unsaturated halogenated alkyl group, halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, Cyanato, isocyanato, thiocyanato, isothiocyanato, silyl, silanol, alkoxy, carbamoyl, thiocarbamoyl, acyloxy, sulfino, phosphinyl, phosphono, phosphonato, hydroxyimino, saturated or unsaturated Examples thereof include a saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group.

  In addition, for example, the 1-position hydrogen atom of the cycloalkoxy group has a substituent such as the above various alkyl groups or aralkyl groups, such as 1-methylcyclohexyloxy group and 2-methyl-2-adamantyloxy group. In the case where an aliphatic polycyclic compound group such as 1-norbornyloxy group or 1-adamantyloxy group is bonded to the oxygen atom at the 1-position, Since the carbon atom directly bonded to the oxygen atom in the group becomes a tertiary carbon atom bonded to the other three carbon atoms, it corresponds to a tertiary alkoxy group described later.

The tertiary alkoxy group is preferably a tertiary alkoxy group having 4 to 20 carbon atoms, more preferably a tertiary alkoxy group having 4 to 15 carbon atoms, from the viewpoint of increasing sensitivity. Preferably, it is a tertiary alkoxy group having 4 to 10 carbon atoms, and is more preferable from the viewpoint of easy availability and the ease of purification.
In addition, it is a tertiary alkoxy group having 1 to 4 carbon atoms in a straight chain hydrocarbon because it is easier to purify by crystallization and a high-purity compound can be obtained in a high yield. Furthermore, it is preferably a tertiary alkoxy group having 1 to 2 linear carbon atoms. Here, the carbon number of the straight chain hydrocarbon in the tertiary alkoxy group represents the carbon number of the straight chain portion in the branched hydrocarbon, for example, the carbon number of the straight chain hydrocarbon in the t-butyloxy group. Is one, and the straight-chain hydrocarbon in the t-amyloxy group has 1 or 2 carbon atoms.

  Examples of the tertiary alkoxy group include, for example, t-butyloxy group, t-amyloxy group, 1,1,3,3, -tetramethylbutoxy group, 1-methylcyclohexyloxy group, 1-decylcyclohexyloxy group, 2-methyl-2-adamantyloxy group, bicyclo [4.3.0] nonanyloxy group, decahydronaphthalenyloxy group, tricyclo [5.2.1.0 (2,6)] decanyloxy group, bornyloxy group, Isobornyloxy group, noradamantyloxy group, 1,7,7-trimethyltricyclo [2.2.1.02,6] heptanyloxy group, 3,7,7-trimethylbicyclo [4.1.0] heptanyloxy group And a polycyclic hydrocarbon group such as a group.

In the chemical formula (1), it is preferable that R ⁶ and / or R ⁷ have a cycloalkoxy group and / or a tertiary alkoxy group which may have a substituent from the viewpoint of achieving high sensitivity.

In particular, in the chemical formula (1), when R ⁶ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, the photosensitive resin composition described later is used as a thick film with high sensitivity. It is preferable in that it is suitable for the case. The photosensitive resin composition to be described later is used not only as a thin film but also as a film or a molded body having a large film thickness of, for example, 10 μm or more. For example, when the photosensitive resin composition is used as a coating material, a sealing material that is a forming material for electronic parts, or a layer forming material, it can be used as a thick film. In particular, in the case of a photosensitive resin composition using an epoxy resin, a thick film having a thickness of 50 μm to several mm may be required depending on the application in order to maintain physical properties such as insulation and barrier properties. Even in the case of a photosensitive resin composition using polyimide having high insulation properties, a thick film of about 10 μm may be required when used as a layer forming material for electronic parts.
However, if a base generator having a large i-line molar extinction coefficient used for exposure is used for a thick film or the like, the base generator in the upper layer part (light irradiation side) of the film absorbs light, and the lower layer of the film. There was a problem that it was difficult to form a pattern because the light did not reach the part. Therefore, the base generator used in the photosensitive resin composition for thick films is required to have low i-line absorption and high sensitivity. In the chemical formula (1), when R ⁶ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, absorption of i-line is relatively small and sensitivity is high. It is suitable as a base generator used in a photosensitive resin composition.

Further, in the chemical formula (1), when R ⁷ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, it tends to be a compound having high sensitivity and good solvent solubility. Therefore, it is preferable in that the base generator is suitable when good solvent solubility is required.

In addition, in the chemical formula (1), when R ⁶ and R ⁷ have a cycloalkoxy group and / or a tertiary alkoxy group which may have a substituent, particularly high sensitivity and good solvent solubility are obtained. It is preferable because it tends to be a compound and has sensitivity to h-line. In this case, the base generator can be applied to a wider range of polymer precursors, and various photosensitive resin compositions can be obtained.

In Chemical Formula ^(1), among the ^{R 5 ~R 8, R 5 ~R} 8 without the an optionally substituted cycloalkoxy group and / or tertiary alkoxy groups are each independently hydrogen, Halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic Groups, which may be the same or different. R ^{5 to} R ⁸ not having a cycloalkoxy group and / or a tertiary alkoxy group which may have the above substituents are independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol. It is preferably a group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group. As the halogen atom or organic group, the same halogen atoms and organic groups as those described above for R ³ and R ⁴ can be used.

In formula (1), R ⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. Here, “deprotectable” means that there is a possibility of changing from —OR ⁹ to —OH. When R ⁹ is hydrogen, the base generator according to the present invention loses the phenolic hydroxyl group by cyclization to change the solubility, and in the case of a basic aqueous solution, the solubility decreases. . Thereby, when the polymer precursor contained in the photosensitive resin composition according to the present invention, which will be described later, is a polyimide precursor or a polybenzoxazole precursor, the solubility decreases due to the reaction of the precursor to the final product. It is possible to increase the solubility contrast between the exposed area and the unexposed area.

In addition, when R ⁹ is a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves, it is deprotected by heating and / or irradiation with electromagnetic waves to generate a hydroxyl group. By protecting the phenolic hydroxyl group with a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves, the compatibility with the compound to be combined, for example, the polymer precursor is improved by appropriately selecting the protecting group, The range of compounds that can be combined is increased. For example, a polymer precursor that is not preferably coexisting with a phenolic hydroxyl group can be used in the resin composition. R ⁹ may be a protecting group for a phenolic hydroxyl group that can be deprotected by heating and / or irradiation with electromagnetic waves under conditions where the amide group present in formula (1) does not decompose in the base generator used in the present invention. As long as it is not particularly limited, it can be used. For example, an amide bond is a strong acid such as boron tribromide or aluminum trichloride, a strong Lewis acid such as sulfuric acid, hydrochloric acid or nitric acid, or a strong base such as sodium hydroxide. Decomposes on heating under basic conditions. Accordingly, such a protecting group that can be deprotected only by heating under strongly acidic or strongly basic conditions is inappropriate as a protecting group used in the base generator of the present invention. R ⁹ is selected as appropriate depending on the type of compound used in combination with the base generator, the application method of the base generator, and the synthesis method for the purpose of improving solubility and compatibility or changing the reactivity during synthesis. It is what is done.

R ⁹ can be selected from a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or an organic group. The organic group in R ⁹ is usually a monovalent organic group.

R ⁹ is an amide present in the formula (1) that is at least one selected from the group consisting of organic groups represented by the following formulas (2-1) to (2-6) It is preferable from the viewpoint that it can be deprotected by heating and / or irradiation with electromagnetic waves under conditions where the group does not decompose.

（式（２−１）中、Ｒ^３０、Ｒ^３１、Ｒ^３２はそれぞれ独立に水素、ハロゲン原子、または有機基であり、Ｒ^３３は有機基であり、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３はそれぞれ互いに結合して環状構造を示していても良い。式（２−２）中、Ｒ^３４は、有機基である。式（２−３）中、Ｒ^３５、Ｒ^３６、Ｒ^３７はそれぞれ独立に水素、ハロゲン原子、または有機基である。式（２−４）中、Ｒ^３８は、有機基である。式（２−５）中、Ｒ^３９は、置換基を有していても良い芳香環である。式（２−６）中、Ｒ^４０は、有機基である。）

(In the formula (2-1), R ³⁰ , R ³¹ and R ³² are each independently hydrogen, a halogen atom or an organic group, R ³³ is an organic group, R ³⁰ , R ³¹ , R ³² and R ³³ may be bonded to each other to represent a cyclic structure, wherein R ³⁴ is an organic group, wherein R ³⁵ , R ³⁶ , and R ³⁷ are each an organic group; Each independently represents a hydrogen atom, a halogen atom, or an organic group, wherein R ³⁸ is an organic group, and R ³⁹ has a substituent in formula (2-5); (In formula (2-6), R ⁴⁰ represents an organic group.)

The organic group represented by the above formula (2-1) can be obtained by a reaction between a hydroxyl group and various vinyl ether compounds. The organic group represented by the formula (2-1) is, for example, a residue of various vinyl ether compounds.
In formula (2-1), R ³⁰ , R ³¹ and R ³² are preferably hydrogen or a substituted or unsubstituted alkyl group, allyl group or aryl group. R ³³ of the organic group represented by the above formula (2-1) is an organic group having 1 or more carbon atoms. R ³³ is exemplified by a group having a hydrocarbon skeleton. The group having a hydrocarbon skeleton may contain a bond or substituent other than a hydrocarbon such as a heteroatom, or such a heteroatom part may be incorporated into an aromatic ring to form a heterocyclic ring. . Examples of the group having a hydrocarbon skeleton include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a linear, branched, or cyclic saturated or unsaturated halogenated alkyl group, or phenyl, naphthyl. An aromatic group such as a group containing an ether bond in a linear or branched saturated or unsaturated hydrocarbon skeleton (for example, — (R—O) _n —R ′, wherein R and R 'Is a substituted or unsubstituted saturated or unsaturated hydrocarbon, n is an integer greater than or equal to 1; -R "-(O-R"') _m , where R "and R"'are substituted or unsubstituted saturated or Unsaturated hydrocarbon, m is an integer of 1 or more,-(O-R "') _m is bonded to a carbon different from the terminal of R"; and the like), linear or branched chain saturation Or a group containing a thioether bond in an unsaturated hydrocarbon skeleton, linear or branched saturated or unsaturated Hydrocarbon backbone onto a cyano group, a silyl group, a nitro group, an acetyl group, and a variety of groups groups having a hetero atom or a hetero atom is bonded, such as acetoxy group. Further, R ³³ of the organic group represented by the above formula (2-1) may be linked to R ³⁰ or R ³¹ to have a cyclic structure.

R ³³ in the formula (2-1) preferably has 1 to 18 carbon atoms from the volatility of the decomposition product, and more preferably 3 to 10 carbon atoms.
R ^{33 in the} formula (2-1) is not particularly limited, and examples thereof include methyl group, ethyl group, ethynyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl. Group, cyclohexylmethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, cyclohexyloxypropyl group, 2- Tetrahydropyranyl group etc. are mentioned. In the formula (2-1), R ³³ is linked to R ³⁰ or R ³¹ to form a cyclic structure, and the substituent bonded to —O— is a cyclic ether such as a 2-tetrahydropyranyl group. Etc.

The organic group represented by the above formula (2-2) can be obtained, for example, by a reaction between a hydroxyl group and a so-called carbonate-based protecting group introduction reagent.
Examples of the carbonate protecting group include tert-butoxycarbonyl group (Boc-), benzyloxycarbonyl group (Z-), 9-fluorenylmethoxycarbonyl (Fmoc-), 1,1-dioxobenzo [b] thiophene- 2-ylmethoxycarbonyl group (Bsmoc-), 2- (4-nitrophenylsulfonyl) ethoxycarbonyl group (Nsc-), p-methoxybenzyloxycarbonyl group (Z (OMe-)), allyloxycarbonyl group (Alloc- ), 2,2,2-trichloroethoxycarbonyl group (Troc-) and the like.

R ^{34 in the} formula (2-2) is not particularly limited, and examples thereof include tert-butyl group, benzyl group, 9-fluorenylmethyl group, 2,2,2-trichloroethyl group, allyl group, p- Examples include methoxybenzyl group, 1,1-dioxobenzo [b] thiophen-2-ylmethyl group, 2- (4-nitrophenylsulfonyl) ethyl group, o-nitrobenzyl group and the like. In the case of an o-nitrobenzyl group, deprotection is possible by irradiation with electromagnetic waves.

The organic group represented by the above formula (2-3) can be obtained, for example, by a reaction between a hydroxyl group and a reagent for introducing a silyl ether protecting group.
Examples of silyl ether protecting groups include trimethylsilyl group (TMS-), tert-butyldimethylsilyl group (TBDMS-), tert-butyldiphenylsilyl group (TBDPS-), triisopropylsilyl group (TIPS-), tert-butoxy. A diphenylsilyl group etc. are mentioned.
Although it does not specifically limit as R ^{< 35>} , R ^<36> , R ^<37 > of said Formula (2-3), For example, alkyl groups, such as a methyl group, a tert-butyl group, an isopropyl group, the aryl group of a phenyl group, and an alkoxy group are suitable Used for.

The organic group represented by the above formula (2-4) can be obtained by, for example, a hydroxyl group and an acid chloride or acid anhydride.
Examples of the ester protecting group represented by the formula (2-4) include an acetyl group (Ac-), a pivaloyl group, and a benzoyl group.
R ^{38 in the} formula (2-4) is not particularly limited, and for example, an alkyl group such as a methyl group or a tert-butyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or the like is preferably used. .

The organic group represented by the above formula (2-5) can be obtained from a hydroxyl group and a halide using, for example, a Williamson reaction.
Examples of the ether protecting group represented by the formula (2-5) include a benzyl group which may have a substituent.
R ^{39 in the} formula (2-5) is an aromatic ring which may have a substituent, and is not particularly limited, and examples thereof include a phenyl group and a naphthyl group which may have a substituent. In particular, when the organic group represented by the formula (2-5) is an o-nitrobenzyl group, that is, when R ³⁹ is a 2-nitrophenyl group, deprotection is possible by electromagnetic wave irradiation.

The organic group represented by the above formula (2-6) can be obtained, for example, by a reaction between a hydroxyl group and an isocyanate.
Examples of the carbamate protecting group include benzyl isocyanate.
Although it does not specifically limit as R of said Formula (2-6), For example, a benzyl group etc. are mentioned.

  Further, the structure represented by the chemical formula (1) has a geometric isomer, but it is preferable to use only the trans isomer. However, cis isomers that are geometric isomers may be mixed during synthesis and purification steps and storage, and in this case, a mixture of trans isomer and cis isomer may be used. It is preferable that the ratio of cis-isomer is less than 10%.

When the base generator represented by the chemical formula (1) is used in combination with a polyimide precursor or a polybenzoxazole precursor, the temperature (5% when the weight is reduced by 5% from the initial weight by heating. % Weight reduction temperature) is preferably 100 ° C. or higher. In the case of a polyimide precursor or a polybenzoxazole precursor, it is necessary to use a high boiling point solvent such as N-methyl-2-pyrrolidone when forming a coating film. Can form a coating film under dry conditions that reduce the influence of the residual solvent. Thereby, the reduction | decrease of the solubility contrast by the influence of a residual solvent in an exposed part and an unexposed part can be suppressed.
In the present invention, 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 (that is, the sample weight becomes 95% of the initial weight). Temperature).
On the other hand, since it is preferable that impurities derived from the base generator of the present invention do not remain in the product using the photosensitive resin composition of the present invention, the base generator of the present invention is a heating process (after development) ( For example, when the polymer to be combined is a polyimide precursor, it is preferably decomposed or volatilized by an imidization process). Specifically, the 5% weight loss temperature of the base generator of the present invention is preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
The 5% weight reduction temperature of the base generator represented by the chemical formula (1) can be adjusted by appropriately selecting the substituent.

  Moreover, it is preferable that the boiling point of the generated base is 25 ° C. or more because the handleability at room temperature is improved. When the boiling point of the generated base is not 25 ° C. or higher, when it is used as a coating film, the amine generated during drying tends to evaporate, which may make the operation difficult. When the generated base is used as a curing accelerator that does not remain in the film, if the weight loss of the generated base at 350 ° C. is 80% or more, the base remains in the cured polymer. It is preferable because it is easy to suppress the above. However, when the generated base is used as a crosslinking agent or a curing agent remaining in the film, the weight reduction of the generated base is not a problem.

The heating temperature for generating a base when using the base generator represented by the chemical formula (1) is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the base generator is placed may be used, and in this case, the base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. From the viewpoint of increasing the reaction rate and generating the base efficiently, the heating temperature for generating the base is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 100 ° C. or higher, Especially preferably, it is 120 degreeC or more. However, depending on the polymer precursors used in combination, for example, the unexposed part may be cured by heating at 60 ° C. or higher, so that the suitable heating temperature is not limited to the above.
Moreover, in order to prevent decomposition | disassembly other than base generation | occurrence | production of the base generator represented by said Chemical formula (1), it is preferable to heat at 300 degrees C or less.

  The base generator represented by the chemical formula (1) generates a base only by irradiation with electromagnetic waves, but generation of the base is promoted by heating appropriately. Therefore, in order to generate a base efficiently, when using the base generator represented by the chemical formula (1), the base is generated by heating after exposure or simultaneously with exposure. Exposure and heating may be performed alternately. The most efficient method is a method of heating simultaneously with exposure.

  Since the base generator represented by the chemical formula (1) can be easily used in combination with other components, the saturation solubility at 25 ° C. of any of the solvents described later is 0.1% by weight or more. It is preferably 0.5% by weight or more. The base generator represented by the chemical formula (1) is, among others, propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2 The saturation solubility at 25 ° C. of one or more solvents selected from the group consisting of polar solvents such as pyrrolidone and γ-butyrolactone, aromatic hydrocarbons such as toluene, and mixed solvents composed of these solvents is 0. The content is preferably 1% by weight or more, and more preferably 0.5% by weight or more. When these solvents, which are good solvents such as polymer precursors, have good solvent solubility as described above, a sufficient amount of the base of the present invention is combined with other components such as polymer precursors. Since the generator can be used, it can sufficiently function as a photobase generator, resulting in an excellent photosensitive resin composition.

As a method for synthesizing the base generator represented by the chemical formula (1) of the present invention, for example, it can be synthesized with reference to Patent Document 6 and JP 2010-254946 A by the present inventors. The protecting group (R ⁹ ) in the phenolic hydroxyl group may be introduced during the synthesis or may be introduced at the end of the synthesis.

Further, among _{R 3} and _{R 4} in the formula (1), when introducing a substituent _{R 4,} firstly, hydroxyphenyl introduced each substituent _{- (C = O) -R 4} ( e.g., _{R 4} Is a methyl group, 2'-hydroxyphenyl methyl ketone having each substituent introduced therein is synthesized. Next, a cinnamic acid derivative into which each substituent is introduced is synthesized by performing a wittig reaction, a Knoevenagel reaction, or a Perkin reaction on hydroxyphenyl- (C═O) —R ₄ into which each substituent is introduced.
When introducing a substituent only into R ₃ among R ₃ and R _{4 in} the formula (1), first, hydroxybenzaldehyde into which each substituent is introduced is synthesized. Next, the methyl group was introduced into R ₃ by changing the reagent of the wittig reaction to hydroxybenzaldehyde into which each substituent was introduced, for example, by changing the reagent to 1-ethoxycarbonylethylidene-triphenylphosphorane or the like and performing the wittig reaction. Synthesis of cinnamic acid derivatives. The reagent for the wittig reaction is appropriately selected depending on the substituent to be introduced into R _3. For example, in the case of an acetyl group, 3-oxo-2- (triphenyl-phosphanylidene) -butyric acid ethyl ester or the like can be used. Using the cinnamic acid derivative thus obtained, the desired product can be obtained in the same manner as described above.

The synthesis of hydroxyphenyl- (C═O) —R ₄ into which each substituent is introduced can be synthesized by performing Friedel-Crafts acylation reaction on the phenol having the corresponding substituent. Further, hydroxyphenyl introduced each substituent - Synthesis of (C = O) -R ₄ is dihydroxyphenyl - (C = O) with respect -R ₄ introducing a substituent by performing Williamson synthesis is also it can. By using dihydroxyphenyl- (C═O) —R ₄ as a starting material to trihydroxy-, tetrahydroxy-, the substituent can be appropriately selected.

After completion of the reaction, the target compound is extracted into an organic solvent, washed with a basic aqueous solution and an acidic aqueous solution, concentrated and dried to obtain a crude product. Then, it is preferable to refine | purify using purification methods, such as the following reprecipitation, crystallization, and recrystallization. The purification method is appropriately selected according to the properties and impurities of the target compound.
In the reprecipitation method, the obtained crude product is dissolved in a small amount of a good solvent to form a solution, and a large amount of the poor solvent is added thereto, or conversely, the solution is gradually added to the large amount of the poor solvent. In this method, the target compound is obtained as a precipitate.
The crystallization method is a method of obtaining a target compound by crystallizing a target component from a solution by cooling or heating utilizing temperature dependency of solubility.
The recrystallization method is a method of obtaining a target compound by dissolving a crude crystal in a solvent and precipitating the crystal by utilizing solvent evaporation, a difference in solubility due to a temperature difference or a change in the mixing ratio of the solvent, and the like.
In addition, the synthesis | combining method of the base generator of this invention is not limited to said method. The base generator of the present invention can be synthesized by a plurality of conventionally known synthesis routes.

  The base generator represented by the chemical formula (1) of the present invention absorbs at least a part of the exposure wavelength in order to sufficiently exhibit the function of base generation for the polymer precursor to be the final product. It is necessary to have. The wavelength of a high-pressure mercury lamp that is a general exposure light source includes 365 nm, 405 nm, and 436 nm. For this reason, it is preferable that the base generator represented by the chemical formula (1) of the present invention absorbs at least one electromagnetic wave having a wavelength of 365 nm, 405 nm, or 436 nm. In such a case, it is preferable because the number of applicable polymer precursors is further increased.

  The base generator represented by the chemical formula (1) has a molar extinction coefficient of 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at 405 nm, and the number of applicable polymer precursors further increases. It is preferable from the point.

The fact that the base generator represented by the chemical formula (1) of the present invention has absorption in the wavelength region is expressed by the chemical formula (1) in a solvent (for example, acetonitrile) that does not absorb in the wavelength region. bases generating agent 1 × ¹⁰ -4 mol / L or less of the concentration ^{(usually, 1 × 10 -4 mol / L~1} × 10 -5 mol / L or so. so as to give suitable absorption intensity, as appropriate, And may be clarified by measuring the absorbance with an ultraviolet-visible spectrophotometer (for example, UV-2550 (manufactured by Shimadzu Corporation)).

Since the base generator represented by the chemical formula (1) according to the present invention has higher sensitivity than the conventionally used photobase generator, various applications are possible. A base such as an acid-base indicator, not limited to combining with a polymer precursor whose reaction to the final product is promoted by heating in the presence of a basic substance or in the presence of a basic substance, which will be described in detail later Thus, various photosensitive compositions can be formed in combination with a compound whose structure and physical properties change. Such a photosensitive composition may be used as a paint, a printing ink, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a micro electro mechanical system (MEMS), an optical member, or an architecture. It can be used as a material forming material.
For example, when an image forming layer is exposed in an image forming medium obtained by coating or impregnating a base material with an image forming layer containing at least a photobase generator and an acid-base indicator, the photobase generator However, the present invention can also be applied to a display device such as an image forming medium in which an image is formed by generating a base that reacts with an acid-base indicator.

<Photosensitive resin composition>
The photosensitive resin composition according to the present invention includes a polymer precursor whose reaction to the final product is promoted by heating with a basic substance or in the presence of the basic substance, and the following chemical formula according to the present invention: It is represented by (1) and contains a base generator that generates a base by irradiation with electromagnetic waves and heating.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は有機基であり、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^１及びＲ^２の少なくとも１つは有機基である。Ｒ^３及びＲ^４はそれぞれ独立に、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基であり、同一であっても異なっていても良い。Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基であり、同一であっても異なっていても良く、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８のいずれかは、置換基を有してもよいシクロアルコキシ基又は３級アルコキシ基を有する。Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それらの２つ以上が結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。Ｒ^９は、水素原子、或いは、加熱及び／又は電磁波の照射により脱保護可能な保護基である。）

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R ¹ and R ² is an organic group, and R ³ and R ⁴ are each independently hydrogen, halogen, Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, which are the same be different even good ^{.R 5, R 6,} R ⁷ and ^{R 8} are each independently hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, two Nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group, may be different even in the same, R ^5, R ⁶ , any one of R ⁷ and R ⁸ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are two or more of them. It may be bonded to form a cyclic structure and may contain a heteroatom bond, and R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves. )

As described above, the base generator represented by the chemical formula (1) has the above-described specific structure, and the (—CR ⁴ ═CR ³ —C (═O) —) moiety is cis by irradiation with electromagnetic waves. Is isomerized to a body and further heated to generate a base (NHR ¹ R ² ). Furthermore, when the base is generated, the structure represented by the chemical formula (1) is cyclized. As a result, the phenolic hydroxyl group is lost, and the solubility of the basic aqueous solution in the developer is lowered.
The polymer precursor is promoted to react with the final product by the action of the basic substance generated from the base generator.

  Due to such a change in solubility of the base generator and the polymer precursor, the photosensitive resin composition according to the present invention has a large difference in solubility between the exposed part and the unexposed part. The characteristic contrast increases, and pattern formation becomes possible.

  As described above, since the base generator represented by the chemical formula (1) has higher sensitivity than the conventional photobase generator, the photosensitive resin composition of the present invention has high sensitivity. In addition, since the photosensitive resin composition of the present invention can adjust solubility in organic solvents and affinity with a polymer precursor to be combined by a substituent or the like, the range of applicable polymer precursors is wide, and the polymer It is widely applied in fields where it is possible to make use of characteristics such as changes in solubility between the precursor and the base generator. For example, it is suitably applied in a field where the characteristics of the photosensitive polyimide precursor resin composition and its imidized product can be utilized. According to the present invention, since the solubility contrast is increased by the change in solubility of the base generator and the polymer precursor, it is possible to suitably use a polyimide precursor that is originally highly soluble in a developer.

Hereinafter, although the structural component of the photosensitive resin composition which concerns on this invention is demonstrated, about the base generator used for the photosensitive resin composition which concerns on this invention, the thing similar to the said base generator concerning this invention is mentioned. Since it can be used, explanation here is omitted. Therefore, the polymer precursor and other components that can be appropriately included as necessary will be described in order.
As the base generator and the polymer precursor, one kind may be used alone, or two or more kinds may be mixed and used.

<Polymer precursor>
The polymer precursor used in the photosensitive resin composition of the present invention means a substance that finally becomes a polymer exhibiting the desired physical properties by reaction, and the reaction includes intermolecular reaction and intramolecular reaction. The polymer precursor itself may be a relatively low molecular compound or a high molecular compound.
The polymer precursor of the present invention is a compound whose reaction to the final product is promoted by a basic substance or by heating in the presence of the basic substance. Here, in the aspect in which the polymer precursor is accelerated by the basic substance or by heating in the presence of the basic substance, the reaction to the final product is accelerated only by the action of the basic substance. In addition to the mode of changing to the final product, the mode includes the mode in which the reaction temperature of the polymer precursor to the final product is lowered by the action of the basic substance as compared to the case where there is no action of the basic substance. .
If there is a reaction temperature difference due to the presence or absence of such a basic substance, an appropriate temperature at which only the polymer precursor coexisting with the basic substance reacts to the final product using the reaction temperature difference. By heating at, only the polymer precursor coexisting with the basic substance reacts with the final product, and the solubility in a solvent such as a developer changes. Therefore, the solubility of the polymer precursor in the solvent can be changed depending on the presence or absence of the basic substance, and thus patterning by development can be performed using the solvent as a developer.

  The polymer precursor of the present invention can be used without particular limitation as long as the reaction to the final product is promoted by the basic substance as described above or by heating in the presence of the basic substance. is there. The following are typical examples, but the invention is not limited to these.

[Polymer precursor that becomes polymer by intermolecular reaction]
Examples of the polymer precursor that becomes a target polymer by intermolecular reaction include a compound having a reactive substituent and a polymerization reaction and a polymer, or a compound that forms a bond (crosslinking reaction) between molecules. And polymers. Examples of the reactive substituent include an epoxy group, an oxetane group, a thiirane group, an isocyanate group, a hydroxyl group, and a silanol group. In addition, the polymer precursor includes a compound that undergoes hydrolysis and polycondensation between molecules, and the reactive substituent includes -SiX of the polysiloxane precursor (where X is an alkoxy group, an acetoxy group, an oxime). And a hydrolyzable group selected from the group consisting of a group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen).

Examples of the compound having a reactive substituent and undergoing a polymerization reaction include a compound having one or more epoxy groups, a compound having one or more oxetane groups, and a compound having one or more thiirane groups. .
Examples of the polymer that has a reactive substituent and undergoes a polymerization reaction include a polymer having two or more epoxy groups (epoxy resin), a polymer having two or more oxetane groups, and two or more thiiranes. And a polymer having a group. The compounds and polymers having an epoxy group are specifically described below, but compounds and polymers having an oxetane group and a thiirane group can also be used in the same manner.

(Compound having epoxy group and polymer)
The compound and polymer having one or more epoxy groups are not particularly limited as long as they have one or more epoxy groups in the molecule, and conventionally known compounds can be used.
The base generator generally also has a function as a curing catalyst for a compound having one or more epoxy groups in the molecule.

When using a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule, two functional groups having reactivity with the epoxy group are contained in the molecule. Two or more compounds may be used in combination. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
Moreover, it is preferable to use what introduce | transduced the said functional group into the polymer side chain of weight average molecular weight 3,000-100,000. If it is less than 3,000, the strength of the film is lowered and tackiness is caused on the surface of the cured film, so that impurities and the like are likely to adhere. On the other hand, if it exceeds 100,000, the viscosity may increase, which is not preferable.

  Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Polyfunctional epoxy resins such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin, There are lysidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc. These epoxy resins may be halogenated and hydrogenated. It may be. As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Industries, Ltd., Eporide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyethylene synthesized from bisphenols and epichlorohydrin) B carboxymethyl having an epoxy group at both ends with polyether; YP series, etc.), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha but Chemical Co. Epo light series, and the like are not limited thereto. Two or more of these epoxy resins may be used in combination. Among these, bisphenol-type epoxy resins are preferable because grades having different molecular weights are widely available as compared with other various epoxy compounds, and adhesiveness and reactivity can be arbitrarily set.

On the other hand, examples of the compound that crosslinks between molecules include a combination of a compound having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule. By the reaction with the hydroxyl group, a urethane bond is formed between the molecules, and the polymer can be formed.
As a polymer that undergoes a cross-linking reaction between molecules, for example, a combination of a polymer having two or more isocyanate groups in the molecule (isocyanate resin) and a polymer having two or more hydroxyl groups in the molecule (polyol) Is mentioned.
A combination of a compound that undergoes a cross-linking reaction between molecules and a polymer may be used. For example, a combination of a polymer (isocyanate resin) having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule, and a compound having two or more isocyanate groups in the molecule Examples include a combination of polymers (polyols) having two or more hydroxyl groups in the molecule.

(Compounds and polymers having isocyanate groups)
As the compound and polymer having an isocyanate group, any known compound can be used without particular limitation as long as it has two or more isocyanate groups in the molecule. As such compounds, in addition to low molecular weight compounds represented by p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, oligomers, A polymer having an isocyanate group in the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more may be used.

(Compounds having a hydroxyl group and polymers)
The compound and polymer having an isocyanate group are usually used in combination with a compound having a hydroxyl group in the molecule. The compound having such a hydroxyl group is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and known compounds can be used. As such a compound, in addition to low molecular weight compounds such as ethylene glycol, propylene glycol, glycerin, diglycerin and pentaerythritol, a polymer having a weight average molecular weight of 3,000 or more has a hydroxyl group in the side chain or terminal. A molecule may be used.

(Polysiloxane precursor)
Examples of the compound that undergoes hydrolysis and polycondensation between molecules include polysiloxane precursors.
As the polysiloxane precursor, Y _n SiX _(4-n) (wherein Y represents an alkyl group, fluoroalkyl group, vinyl group, phenyl group, or hydrogen which may have a substituent, A hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen, where n is an integer from 0 to 3. And the hydrolyzed polycondensate of the organosilicon compound. Among these, those in which n is 0 to 2 in the above formula are preferable. In addition, the hydrolyzable group is preferably an alkoxy group because the silica-dispersed oligomer solution is easily prepared and easily available.
There is no restriction | limiting in particular as said organosilicon compound, A well-known thing can be used. For example, trimethoxysilane, triethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-butoxysilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane , N-propyltriethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane , Diphenyldimethoxysilane, vinyltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, fluoroalkylsilanes known as fluorine-based silane coupling agents, and their hydrolysis condensates or cohydrolysis condensates; and mixtures thereof.

[Polymer precursor that becomes polymer by intramolecular ring-closing reaction]
Examples of the polymer precursor that finally becomes a polymer that exhibits the desired physical properties by the intramolecular ring-closing reaction include a polyimide precursor and a polybenzoxazole precursor. These precursors may be a mixture of two or more separately synthesized polymer precursors.
Hereinafter, although the polyimide precursor and polybenzoxazole precursor which are the preferable polymer precursors of this invention are demonstrated, this invention is not limited to these.

(Polyimide precursor)
As the polyimide precursor, a polyamic acid having a repeating unit represented by the following chemical formula (5) is preferably used.

(In the chemical formula (5), R ¹¹ is a tetravalent organic group. R ¹² is a divalent organic group. R ¹³ and R ¹⁴ are a hydrogen atom or a monovalent organic group. (It is a natural number of 1 or more.)

Examples of the case where R ¹³ and R ¹⁴ are monovalent organic groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and C _n H _2n OC _m H _{2m + 1} containing an ether bond in these groups. The structure represented can be mentioned.
As the polyimide precursor, a polyamic acid in which R ¹³ and R ¹⁴ are hydrogen atoms is preferably used from the viewpoint of alkali developability.

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.

  Polyamic acid is preferable because it can be obtained by simply mixing acid dianhydride and diamine in a solution, so that it can be synthesized by a one-step reaction, and can be synthesized easily and at low cost.

  As a secondary effect, when the polymer precursor to be used is a polyamic acid, the final curing temperature is less than 300 ° C., more preferably because the temperature required for imidization is low due to the catalytic effect of the basic substance. It can be lowered to 250 ° C. or lower. In order to imidize the conventional polyamic acid, the final cure temperature had to be 300 ° C. or higher, so the use was limited. However, it became possible to lower the final cure temperature, so a wider range Applicable to usage.

Polyamic acid is obtained by the reaction of acid dianhydride and diamine. From the viewpoint of imparting excellent heat resistance and dimensional stability to the finally obtained polyimide, in the chemical formula (5), R ¹¹ or R ¹² Is preferably an aromatic compound, and R ¹¹ and R ¹² are more preferably aromatic compounds. At this time, in R ¹¹ of the chemical formula (5), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ¹¹ may be bonded to the same aromatic ring. May be bonded to different aromatic rings. Similarly, in R ¹² of the chemical formula (5), two groups ((—NH—) ₂ ) bonded to R ¹² may be bonded to the same aromatic ring or bonded to different aromatic rings. You may do it.

  The polyamic acid represented by the chemical formula (5) may be composed of a single repeating unit or may be composed of two or more repeating units.

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

  Examples of the acid dianhydride applicable to the reaction for obtaining the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane. Aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride and 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 Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarboxylic acid Anhydride, 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-di Carboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride, , 3-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [ 4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride,

2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-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, p-phenylenediamine,
m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl Sulfide, 4,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4 ′ -Diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2 , 2-Di (4-aminophenyl) propa 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2, 2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1, 3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-amino Phenyl) -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- (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1, 4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1 , 4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α -Ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylben) L) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) Pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4 -Aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-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 Such as 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, etc. 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 -Aliphatic amines 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, There exists what is represented by following Chemical formula (6). Specific examples include benzidine and the like.

  (In the chemical formula (6), a is a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.)

Furthermore, in the chemical formula (6), a diamine having a substituent at a position where the amino group on the benzene ring is not substituted and which is not involved in the bond with another benzene ring can also be used. These substituents are 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 a wholly aromatic polyimide.

<Polybenzoxazole precursor>
As the polybenzoxazole precursor used in the present invention, a polyamide alcohol having a repeating unit represented by the following chemical formula (7) is preferably used.

  Polyamide alcohol can be synthesized by a conventionally known method. For example, it can be obtained by addition reaction of a dicarboxylic acid derivative such as a dicarboxylic acid halide and dihydroxydiamine in an organic solvent.

(In the chemical formula (7), R ¹⁵ is a divalent organic group. R ¹⁶ is a tetravalent organic group.)

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

The polyamide alcohol having a repeating unit represented by the chemical formula (7) gives excellent heat resistance and dimensional stability to the finally obtained polybenzoxazole. In the chemical formula (7), R ¹⁵ or R ¹⁶ is preferably an aromatic compound, and R ¹⁵ and R ¹⁶ are more preferably aromatic compounds. At this time, in R ¹⁵ of the chemical formula (7), two groups (—CO—) ₂ bonded to the R ¹⁵ may be bonded to the same aromatic ring or bonded to different aromatic rings. May be. Similarly, in R ¹⁶ of the chemical formula (7), four groups ((—NH—) ₂ (—OH) ₂ ) bonded to R ¹⁶ may be bonded to the same aromatic ring, It may be bonded to different aromatic rings.

  The polyamide alcohol represented by the chemical formula (7) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.

  Examples of the dicarboxylic acid and its derivatives applicable to the reaction for obtaining the polybenzoxazole precursor include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-benzophenone dicarboxylic acid, and 3,4′-benzophenone dicarboxylic acid. Acid, 3,3′-benzophenone dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 3,4′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4 '-Diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 3,4'-diphenyl sulfone dicarboxylic acid, 3,3'-diphenyl sulfone dicarboxylic acid, 4,4'- Hexafluoroisopropylidene dibenzoic acid, 4 4′-dicarboxydiphenylamide, 1,4-phenylenediethanoic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,2-trifluoroethane, bis (4-carboxyphenyl) Tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5 -Fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis- (p-carboxyphenyl) propane, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 2,6-naphthalenedicarboxylic acid, or These acid halides and active esters with hydroxybenzotriazole, etc. It can be exemplified, but the invention is not limited thereto. These may be used alone or in combination of two or more.

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

Polymer precursors such as polyimide precursors and polybenzoxazole precursors have a film thickness of 1 μm in order to increase the sensitivity of the photosensitive resin composition and obtain a pattern shape that accurately reproduces the mask pattern. Furthermore, it is preferable that the transmittance is at least 5% or more with respect to the exposure wavelength, and it is more preferable that the transmittance is 15% or more.
The high transmittance of polymer precursors such as polyimide precursors and polybenzoxazole precursors with respect to the exposure wavelength means that there is little loss of electromagnetic waves, and a highly sensitive photosensitive resin composition is used. Can be obtained.

  In addition, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a transmittance with respect to an electromagnetic wave having a wavelength of at least 436 nm, 405 nm, and 365 nm is formed on a film having a thickness of 1 μm. Is preferably 5% or more, more preferably 15%, particularly preferably 50% or more.

  The weight average molecular weight of a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor is preferably in the range of 3,000 to 1,000,000, although it depends on the application, 5,000 to 500. Is more preferably in the range of 10,000 to 500,000. When the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when heat treatment 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, the solubility tends to decrease, and it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.

  The molecular weight used here is a value in terms of polystyrene measured by gel permeation chromatography (GPC), which may be the molecular weight of a polymer precursor itself such as a polyimide precursor, or chemical imidization with acetic anhydride or the like. It may be after processing.

  In addition, the solvent at the time of the polyimide precursor or polybenzoxazole precursor synthesis is preferably a polar solvent, and representative examples thereof include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, and N, N-dimethylformamide. , N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoamide, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetra Examples include methylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, 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.

  Since the solubility of polyamic acid and polybenzoxazole precursor decreases due to the reaction to the final product by the action of the basic substance, the base generation of the base generator represented by the chemical formula (1) By combining with a decrease in solubility, the photosensitive resin composition of the present invention has an advantage that the solubility contrast between the exposed portion and the unexposed portion can be further increased.

<Other ingredients>
The photosensitive resin composition according to the present invention may be a simple mixture of the base generator represented by the chemical formula (1), one or more kinds of polymer precursors, and a solvent. Alternatively, a photosensitive resin composition may be prepared by blending a thermosetting component, a non-polymerizable binder resin other than the polymer precursor, and other components.

  Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition. Moreover, when using polyamic acid as a precursor, you may use the solution obtained by the synthesis reaction of polyamic acid as it is, and may mix other components there as needed.

  Examples of general-purpose solvents that can be used include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene glycol mono Glycol monoethers (so-called cellosolves) such as ethyl 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, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), propylene Esters such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 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, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o- Halogenated hydrocarbons such as chlorobenzene and m-dichlorobenzene; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide and the like Amides of N; pyrrolidones such as N-methyl-2-pyrrolidone and N-acetyl-2-pyrrolidone; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, dimethyl sulfone, Examples include sulfones such as tetramethylene sulfone and dimethyltetramethylene sulfone, phosphoric acid amides such as hexamethylphosphoamide, and other organic polar solvents, and aromatics such as benzene, toluene, xylene, and pyridine. Hydrocarbons and their Other organic nonpolar solvents are also included. These solvents are used alone or in combination.

  Among them, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene, etc. Aromatic hydrocarbons and mixed solvents composed of these solvents are preferred.

  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.

As long as the effect of the present invention is not hindered, the photosensitive resin composition of the present invention may contain other photosensitive components that generate an acid or a base by light as an auxiliary role of the base generator of the present invention. good. Further, a base proliferating agent or a sensitizer may be added.
Examples of the compound that generates an acid by light include photosensitive diazoquinone compounds having a 1,2-benzoquinone diazide or 1,2-naphthoquinone diazide structure. US Pat. Nos. 2,772,972, No. 213, No. 3,669,658. Further, known photoacid generators such as triazine and derivatives thereof, sulfonic acid oxime ester compounds, sulfonic acid iodonium salts, and sulfonic acid sulfonium salts can be used. Examples of the compound that generates a base by light include 2,6-dimethyl-3,5-dicyano-4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl. Examples include -4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. it can.

A base proliferating agent that generates a base by a decomposition or rearrangement reaction by the action of a small amount of base generated from the base generator may be used in combination. Examples of the base proliferating agent include a compound having 9-fluorenylmethyl carbamate bond, 1,1-dimethyl-2-cyanomethyl carbamate bond ((CN) CH ₂ C (CH ₃ ) ₂ OC (O) NR ₂ ), Compounds having a paranitrobenzyl carbamate bond, compounds having a 2,4-dichlorobenzyl carbamate bond, and other urethane compounds described in paragraphs 0010 to 0032 of JP 2000-330270 A And urethane compounds described in paragraphs 0033 to 0060 of JP-A-2008-250111.

Addition of a sensitizer may be effective when it is desired to make the base generator sufficiently use the energy of electromagnetic waves having a wavelength that passes through the polymer to improve sensitivity.
In particular, when the absorption of the polyimide precursor is also at a wavelength of 360 nm or more, the effect of adding a sensitizer is great. Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, coumarins and derivatives thereof, ketocoumarin and derivatives thereof, ketobiscoumarin and derivatives thereof, cyclopentanone and derivatives thereof , Cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, thioxanthene series, xanthene series and derivatives thereof.

Specific examples of coumarin, ketocoumarin and derivatives thereof include 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. Furthermore, benzophenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1,2-benzanthraquinone, 1,2-naphthoquinone, etc. Is mentioned.
Since these exhibit a particularly excellent effect in combination with a base generator, a sensitizer exhibiting an optimal sensitizing action is appropriately selected depending on the structure of the base generator.

  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 polymer precursor (solid content) is based on the entire solid content of the photosensitive resin composition from the viewpoint of film physical properties of the pattern to be obtained, particularly film strength and heat resistance. 30% by weight or more, preferably 50% by weight or more.
The base generator represented by the chemical formula (1) is usually 0.1 to 95% by weight, preferably 0.5 to 60% by weight based on the solid content of the polymer precursor contained in the photosensitive resin composition. %. If it is less than 0.1% by weight, the solubility contrast between the exposed part and the unexposed part may not be sufficiently increased, and if it exceeds 95% by weight, the properties of the finally obtained cured resin will be reflected in the final product. It is hard to be done.
When used as a curing agent, such as when combined with an epoxy compound, it is usually contained in the range of 0.1 to 95% by weight, preferably 0.5 to 60% by weight, depending on the degree of curing.
On the other hand, when used as a curing accelerator, it can be cured with a small amount of addition, and the base generator represented by the chemical formula (1) is a solid content of the polymer precursor contained in the photosensitive resin composition. On the other hand, it is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight.

In the photosensitive resin composition according to the present invention, the polymer precursor (solid content) is usually 50.1 to 99.9% by weight, further 62.5% based on the entire solid content of the photosensitive resin composition. It is preferably ˜99.5% by weight. The base generator represented by the chemical formula (1) is usually 0.1 to 49.9% by weight, more preferably 0.5 to 37.5% by weight, based on the entire solid content of the photosensitive resin composition. It is preferable that
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.

  Moreover, the mixture ratio of arbitrary components other than a solvent has the preferable range of 0.1 weight%-95 weight% with respect to the whole solid content of the photosensitive resin composition. When the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when it exceeds 95% by weight, the properties of the finally obtained resin cured product are not easily reflected in the final product.

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

  When a polyimide precursor or a polybenzoxazole precursor is used as a polymer precursor as an embodiment of the photosensitive resin composition of the present invention, the resulting polyimide and polybenzoxazole have heat resistance, dimensional stability, and insulating properties. From the viewpoint of securing the above properties, the 5% weight loss temperature measured in nitrogen of the polyimide and polybenzoxazole 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.

  The glass transition temperature of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance, but in applications where a thermoforming process is considered like an optical waveguide, It preferably exhibits a glass transition temperature of about 120 ° C. to 450 ° C., more preferably about 200 ° C. to 380 ° C.

  Here, the glass transition temperature in the present invention is tan δ (tan δ = loss elastic modulus (tan δ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape. E ″) / determined from the peak temperature of the storage elastic modulus (E ′). As the dynamic viscoelasticity measurement, for example, the frequency is increased by 3 Hz using a viscoelasticity measuring device Solid Analyzer RSA II (manufactured by Rheometric Scientific) If the polyimide and polybenzoxazole obtained from the photosensitive resin composition cannot be formed into a film shape, the temperature is determined by the inflection point of the baseline of differential thermal analysis (DTA). To do.

  From the viewpoint of the dimensional stability of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention, the linear thermal expansion coefficient is preferably 60 ppm or less, and more preferably 40 ppm or less. In the case of forming a film on a silicon wafer in a manufacturing process of a semiconductor element or the like, 20 ppm or less is more preferable from the viewpoint of adhesion and warpage of the substrate.

The linear thermal expansion coefficient in this invention can be calculated | required with the thermomechanical analyzer (TMA) of the film of the polyimide and polybenzoxazole obtained from the photosensitive resin composition obtained by this invention. Using a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku Corporation), the heating rate is 10 ° C./min, and the tensile load is 1 g / 25,000 μm so that the weight per cross-sectional area of the evaluation sample is the same. ² is obtained.

As described above, according to the present invention, the photosensitive resin composition can be obtained by a simple method of simply mixing the base generator represented by the chemical formula (1) with the polymer precursor. Excellent cost performance.
The aromatic component-containing carboxylic acid constituting the base generator represented by the chemical formula (1) and the basic substance can be obtained at low cost, and the price as the photosensitive resin composition can be suppressed.
The photosensitive resin composition according to the present invention can be applied to promote the reaction of a wide variety of polymer precursors to the final product by the base generator represented by the chemical formula (1). The structure of the resulting polymer can be selected from a wide range.
Furthermore, since the base generator represented by the chemical formula (1) is cyclized when the base is generated and the phenolic hydroxyl group disappears, the solubility in a developer such as a basic solution is changed, and the polymer precursor is changed. In the case of a polyimide precursor, a polybenzoxazole precursor or the like, it helps to lower the solubility of the photosensitive resin composition and contributes to the improvement of the solubility contrast in the exposed and unexposed areas.
Also, due to the catalytic effect of amines and other basic substances generated by electromagnetic wave irradiation, the processing temperature required for reactions such as cyclization such as imidation from polyimide precursors or polybenzoxazole precursors to final products is reduced. Therefore, it is possible to reduce the load on the process and damage to the product due to heat.
Furthermore, since the base generator of the present invention that generates a base by irradiation and heating of electromagnetic waves includes a heating step in the step of obtaining a final product from the polymer precursor, the heating step can be used. The amount can be reduced, and the process can be effectively used.

  For the photosensitive resin composition according to the present invention, resin materials such as printing ink, paint, sealant, adhesive, electronic material, optical circuit component, molding material, resist material, building material, stereolithography, and optical member are used. It can be used for all known fields and products. It can be suitably used both for applications that are used by exposing the entire surface, such as paints, sealants, and adhesives, and for applications that form patterns such as permanent films and release films.

  The photosensitive resin composition according to the present invention can be used in a wide range of fields, products such as heat resistance, dimensional stability, and insulation, such as paints, printing inks, sealants, or adhesives, or It is suitably used as a forming material for a display device, a semiconductor device, an electronic component, a micro electro mechanical system (MEMS), an optical member or a building material. For example, specifically, as a forming material for an electronic component, a sealing material and a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring covering film, and the like. In addition, as a forming material of a display device, a layer forming material or an image forming material can be used for a color filter, a film for flexible display, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, a resist material, a layer forming material such as a buffer coat film, or the like can be used. Further, as a material for forming an optical component, it can be used as an optical material or a layer forming material for a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, or the like. Moreover, as a building material, it can use for a coating material, a coating agent, etc. It can also be used as a material for an optically shaped object. A printed matter, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped article, an optical member, or a building material is provided.

  Since it has the above characteristics, the photosensitive resin composition according to the present invention can also be used as a pattern forming material. In particular, when a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is used as a pattern forming material (resist), the pattern formed thereby is a permanent film made of polyimide or polybenzoxazole. Functions as a component that imparts heat resistance and insulation, such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, etc. It is suitable for forming an optical member or an electronic member.

<Relief pattern manufacturing method>
The method for producing a relief pattern according to the present invention comprises forming a coating film or a molded body comprising the photosensitive resin composition according to the present invention, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, Development is performed after heating or simultaneously with irradiation to change the solubility of the irradiated portion.

  The photosensitive resin composition according to the present invention is coated on some support to form a coating film, or a molded body is formed by a suitable molding method, and the coating film or molded body is formed into a predetermined pattern shape. Is irradiated with electromagnetic waves and heated at the same time as irradiation or irradiation, the base generator represented by the above chemical formula (1) is isomerized and cyclized only in the exposed portion to produce a basic substance. The basic substance acts as a catalyst that promotes the reaction of the polymer precursor in the exposed area to the final product.

In the case of using a polymer precursor whose thermal curing temperature is lowered by the catalytic action of a base, such as a polyimide precursor or a polybenzoxazole precursor, first, such a polymer precursor and the chemical formula (1) The part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base generator represented by these is exposed. When heated after exposure or simultaneously with exposure, a basic substance is generated in the exposed portion, and the thermosetting temperature of that portion is selectively lowered. After the exposure or simultaneously with the exposure, the exposed portion is heat-cured but the unexposed portion is heated at a processing temperature that is not heat-cured, and only the exposed portion is cured. The heating step for generating the basic substance and the heating step (post-exposure bake) for performing the reaction for curing only the exposed portion may be the same step or different steps.
Next, the unexposed portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  Further, even when using a polymer precursor that initiates the reaction by the catalytic action of a base, such as a compound having an epoxy group or a cyanate group and a polymer, first, such a polymer precursor, and The part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base generator represented by the said Chemical formula (1) is exposed. When it is heated after exposure or simultaneously with exposure, a basic substance is generated in the exposed area, the reaction of the compound having an epoxy group or cyanate group and a polymer in that area is initiated, and only the exposed area is cured. The heating step for generating the basic substance and the heating step (post-exposure bake) for performing the reaction for curing only the exposed portion may be the same step or different steps. Next, the unexposed portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  The photosensitive resin composition of the present invention includes propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. After dissolving in polar solvents such as toluene, aromatic hydrocarbons such as toluene, and mixed solvents composed of these solvents, immersion method, spray method, flexographic printing method, gravure printing method, screen printing method, spin coating method, dispensing It can be applied to the surface of a substrate such as a silicon wafer, metal substrate, ceramic substrate or resin film by a method, etc., and heated to remove most of the solvent to give a non-adhesive coating on the surface of the substrate. it can. 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 exposed to an electromagnetic wave through a mask having a predetermined pattern to be exposed in a pattern, and after heating, the unexposed portion of the film is developed and removed with an appropriate developer to obtain a desired pattern. Can be obtained.

  The exposure method and the exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure. A contact / proximity exposure machine using a g-line stepper, i-line stepper, ultrahigh pressure mercury lamp, or mirror projection exposure machine. Alternatively, a projector or a radiation source that can irradiate ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

The heating temperature for generating a heated base after exposure or simultaneously with exposure is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the photosensitive resin composition is placed may be used, and in that case, a base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. From the viewpoint of increasing the reaction rate and efficiently generating amine, the heating temperature for generating the base is preferably 30 ° C or higher, more preferably 60 ° C or higher, still more preferably 100 ° C or higher, Especially preferably, it is 120 degreeC or more. However, depending on the polymer precursors used in combination, for example, the unexposed part may be cured by heating at 60 ° C. or higher, so that the suitable heating temperature is not limited to the above.
For example, in the case of an epoxy resin, a preferable heat treatment temperature range is appropriately selected depending on the type of the epoxy resin, but is usually about 100 ° C to 150 ° C.

The coating film of the photosensitive resin composition according to the present invention is a post-exposure bake (Post) between the exposure process and the development process in order to physically accelerate the cross-linking reaction or to perform a reaction to cure only the exposed area. It is preferable to perform Exposure Bake (PEB). The PEB is a temperature at which the reaction rate of the curing reaction such as the imidization rate differs between the site where the base is present and the site where the base is not present without irradiation due to the action of the base generated by electromagnetic wave irradiation and heating. It is preferable to carry out with. For example, in the case of imidization, the preferable heat treatment temperature range is usually about 60 ° C to 200 ° C, more preferably 120 ° C to 200 ° C. When the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to cause a difference in the imidization ratio between the exposed portion and the unexposed portion under realistic process conditions. On the other hand, when the heat treatment temperature exceeds 200 ° C., imidization may proceed even in an unexposed portion where no amine is present, and it is difficult to cause a difference in solubility between the exposed portion and the unexposed portion.
This heat treatment may be any method as long as it is a known method, and specific examples thereof include heating with a circulating oven in a nitrogen atmosphere or a hot plate, or the like, but is not particularly limited.
In the present invention, a base is generated from the base generator by irradiation with electromagnetic waves and heating. The heating and PEB process for generating the base may be the same process or separate processes.

(Developer)
The developer used in the development step is not particularly limited as long as the solvent that changes the solubility of the irradiation site is used as the developer, and is appropriately selected according to the polymer precursor to be used, such as a basic aqueous solution or an organic solvent. It is possible to select.

Although it does not specifically limit as basic aqueous solution, For example, other than tetramethylammonium hydroxide (TMAH) aqueous solution whose density | concentration is 0.01 weight%-10 weight%, Preferably, 0.05 weight%-5 weight%. , Diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl Examples of the aqueous solution include methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and tetramethylammonium.
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, Alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone and methyl ethyl ketone, other tetrahydrofuran, chloroform, acetonitrile, etc. Or you may add in combination of 2 or more types. After development, washing is performed with water or a poor solvent. 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, a patterned high heat resistant resin layer is formed by heating at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several tens of minutes to several hours. The

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified. The produced base generator was confirmed in chemical structure by ¹ H NMR measurement.
Moreover, each measurement and experiment were performed using the apparatus shown below.
¹ H NMR measurement: JEOL JNM-LA400WB, manufactured by JEOL Ltd.
Manual exposure: manufactured by Dainippon Kaken, MA-1100
Absorbance measurement: UV-2550 manufactured by Shimadzu Corporation, UV-visible spectrophotometer
5% weight loss temperature measurement: manufactured by Shimadzu Corporation, simultaneous differential heat / thermogravimetric measurement device DTG-60

(Production Example 1: Synthesis of base generator (1))
Under a stream of argon, 17.5 g (127 mmol) of 2,4-dihydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 49.4 g (304 mmol) of bromocyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.), dimethylformamide ( 196 ml of Kanto Chemical Co., Ltd.) was added and stirred, 30.44 g (304 mmol) of potassium hydrogen carbonate (Kanto Chemical Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 15 hours. The reaction solution was allowed to cool, filtered and concentrated, and then purified by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1 (volume ratio)) to obtain 3.15 g of aldehyde derivative A.
In a 100 mL flask, 1.00 g of potassium carbonate (Kanto Chemical Co., Ltd.) was added to 15 mL of methanol (Kanto Chemical Co., Ltd.). In a 50 mL flask, 2.18 g (5.09 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.12 g (5.09 mmol) of the aldehyde derivative A obtained above were methanol. Dissolve in 10 mL and slowly add dropwise to a well-stirred potassium carbonate solution. After stirring for 3 hours, the completion of the reaction was confirmed by TLC, followed by filtration to remove potassium carbonate and concentration under reduced pressure. After concentration, 12 mL of 1N aqueous sodium hydroxide solution was added and stirred for 3 hours. After completion of the reaction, triphenylphosphine oxide was removed by filtration, and then concentrated hydrochloric acid was added dropwise to acidify the reaction solution. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 940 mg of cinnamic acid derivative B. Subsequently, in a 100 mL three-necked flask, 940 mg (3.57 mmol) of cinnamic acid derivative B was dissolved in 10 mL of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.), and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride ( EDC) (Tokyo Chemical Industry Co., Ltd.) 0.821 g (4.28 mmol) was added. After 30 minutes, 0.42 ml (4.28 mmol) of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with chloroform, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, and concentrated. Thereafter, 10 mL of methanol (manufactured by Kanto Chemical Co., Inc.) was added and dissolved by heating at 60 ° C., and then cooled and crystallized. After cooling with ice, the precipitated crystals were washed with a small amount of cooled methanol to obtain 820 mg of a base generator (1) represented by the following formula (11) (yield 70%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Production Example 2: Synthesis of base generator (2))
In Production Example 1, it is represented by the following chemical formula (12) in the same manner as in Production Example 1 except that equimolar amounts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) are used as the base component instead of piperidine. The base generator (2) was obtained (yield 68%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Production Example 3: Synthesis of base generator (3))
In Production Example 1, it is represented by the following chemical formula (13) in the same manner as in Production Example 1 except that equimolar amounts of butylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) are used instead of piperidine as the base component. The base generator (3) was obtained (yield 75%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Production Example 4: Synthesis of base generator (4))
In Production Example 1, instead of using piperidine as a base component, the same chemical formula as in Production Example 1 was used except that 3-amino-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in an equimolar amount. The base generator (4) represented by (14) was obtained (61% yield). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Production Example 5: Synthesis of base generator (5))
In the same manner as in Production Example 1, cinnamic acid derivative B was obtained.
Subsequently, 836 mg (3.19 mmol) of cinnamic acid derivative B was dissolved in 10 mL of dehydrated dimethylformamide in a 100 mL three-necked flask under a nitrogen atmosphere, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved in an ice bath. 0.73 g (3.83 mmol, 1.2 eq) of salt (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, 178 mg (1.53 mmol, 0.48 eq) of 1,6-diaminohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with chloroform, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, and concentrated. Thereafter, 10 mL of methanol (manufactured by Kanto Chemical Co., Inc.) was added and dissolved by heating at 60 ° C., and then cooled and crystallized. After cooling with ice, the precipitated crystals were washed with a small amount of cooled methanol to obtain 580 mg of a base generator (5) represented by the following formula (15) (yield 30%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed. In addition, when using diamine, since the reaction point becomes two places and the yield of elementary reaction influences, a yield becomes low compared with the case where monoamine is used.

(Production Example 6: Synthesis of base generator (6))
In Production Example 5, in the same manner as in Production Example 6 except that equimolar amount of p-xylylenediamine (Tokyo Chemical Industry Co., Ltd.) was used instead of 1,6-diaminohexane, the following chemical formula (16) (6) was obtained (yield 34%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Production Example 7: Synthesis of base generator (7))
In Production Example 7, instead of 1,6-diaminohexane, p-xylylenediamine (Tokyo Chemical Industry Co., Ltd.) was used in an equimolar amount in the same manner as in Production Example 6, and the following chemical formula (17) (7) was obtained (yield 28%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Comparative Production Example 1: Synthesis of Comparative Base Generator (1))
In Production Example 1, the same chemical formula as in Production Example 1 was used except that 2-hydroxy-4-methoxybenzaldehyde (Tokyo Chemical Industry Co., Ltd.) was used in an equimolar amount instead of 2,4-dihydroxybenzaldehyde. A comparative base generator (1) represented by (18) was obtained.
Crystallization was conducted in the same manner as in Production Example 1. As a result, the yield was 46%. When the structure was confirmed by NMR, it was found that 0.5% impurities were contained. The comparative base generator (1) was obtained by performing the crystallization operation again (43% yield). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Comparative Production Example 2: Synthesis of Comparative Base Generator (2))
In Comparative Production Example 1, a crude product was obtained in the same manner as in Comparative Production Example 1 except that equimolar amounts of butylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were used as the base component instead of piperidine. . By repeating the same crystallization operation as in Production Example 1 twice, a comparative base generator (2) represented by the following chemical formula (19) was obtained (yield 40%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Comparative Production Example 3: Synthesis of Comparative Base Generator (3))
In Production Example 5, crude production was performed in the same manner as in Production Example 5 except that 2-hydroxy-4-methoxybenzaldehyde (Tokyo Chemical Industry Co., Ltd.) was used in an equimolar amount instead of 2,4-dihydroxybenzaldehyde. I got a thing. By repeating the same crystallization operation as in Production Example 1 twice, a comparative base generator (3) represented by the following chemical formula (20) was obtained (yield 21%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

(Comparative Production Example 4: Synthesis of Comparative Base Generator (4))
In Production Example 1, a crude product was obtained in the same manner as in Production Example 1 except that an equimolar amount of 2-bromobutane (Tokyo Chemical Industry Co., Ltd.) was used instead of bromocyclohexane. By repeating the same crystallization operation as in Production Example 1 twice, a comparative base generator (4) represented by the following chemical formula (21) was obtained (yield 38%). The synthesis of the target compound was confirmed by NMR, and no impurities were confirmed.

<Evaluation of base generator>
The synthesized base generators (1) to (7) and comparative base generators (1) to (4) were measured and evaluated as follows. The results of molar extinction coefficient and 5% weight loss temperature are shown in Table 1.
(1) Molar extinction coefficient The base generators (1) to (7) and the comparative base generators (1) to (4) were dissolved in acetonitrile at a concentration of 1 × 10 ⁻⁴ mol / L, respectively. The solution was filled in (optical path length 10 mm), and the absorbance at 365 nm was measured. The molar extinction coefficient ε is a value obtained by dividing the absorbance of the solution by the thickness of the absorption layer and the molar concentration of the solute.

(2) 5% weight loss temperature In order to evaluate the heat resistance of the base generators (1) to (7) and the comparative base generators (1) to (4), the temperature was increased at a rate of 10 ° C / min. The 5% weight loss temperature was measured.

(3) i-line sensitivity i-line sensitivity was evaluated using NMR measurement. In addition, i-line sensitivity is the exposure amount in i-line conversion required for 50% isomerization.
For the base generators (1) to (7) and the comparative base generators (1) to (4), 1 mg of a sample was dissolved in 0.5 mL of heavy dimethyl sulfoxide in a quartz NMR tube.
A filter that cuts light of 350 nm or less for the base generators (1) to (7) and the comparative base generators (1) to (4) (trade name: GG385, thickness 1 mm, manufactured by Shibuya Optical Co., Ltd.) And a high-pressure mercury lamp were used for intermittent light irradiation, ¹ H NMR was measured, the isomerization ratio was measured, and the irradiation amount at which the isomerization ratio was 50% was determined. Table 2 shows the irradiation dose at which the isomerization rate is 50%.

(Synthesis Example 1: Synthesis of polyimide precursor (1))
10.0 g (50 mmol) of di (4-aminophenyl) ether was put into a 300 mL three-necked flask, dissolved in 105.4 mL of dehydrated N, N-dimethylacetamide (DMAc), and an ice bath under a nitrogen stream. The mixture was stirred while cooling. Thereto, 14.7 g (50 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added little by little. After completion of the addition, the mixture was stirred in an ice bath for 5 hours, and the solution was dehydrated. The precipitate was re-precipitated with diethyl ether, and the precipitate was dried at room temperature under reduced pressure for 17 hours to quantitatively obtain a polyamic acid (polyimide precursor (1)) having a weight average molecular weight of 10,000 as a white solid.

(Synthesis Example 2: Synthesis of metal alkoxide condensate)
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.05 g of ammonia water, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours using a mantle heater. Subsequently, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate (alkoxysilane condensate (1)).

(Example 1: Preparation of photosensitive resin composition (1))
A photosensitive resin composition (1) having the composition shown below was prepared.
Polyimide precursor (1): 100 parts by weight Base generator (1): 15 parts by weight Solvent (NMP (N-methylpyrrolidone)): 843 parts by weight

(Examples 2 to 4: Preparation of photosensitive resin compositions (2) to (4))
In Example 1, photosensitive resin compositions (2) to (4) were used in the same manner as in Example 1 except that base generators (2) to (4) were used instead of the base generator (1). ) Was prepared.

(Comparative Example 1: Preparation of comparative photosensitive resin composition (1))
A comparative photosensitive resin composition (1) was prepared in the same manner as in Example 1 except that the comparative base generator (1) was used instead of the base generator (1) in Example 1.

(Creation of coating film)
The photosensitive resin composition (1) and the comparative photosensitive resin composition (1) were each spin-coated on a chrome-plated glass so as to have a final film thickness of 13.5 μm, and then on a hot plate at 100 ° C. Were dried for 15 minutes to obtain 9 coating films of the photosensitive resin composition (1) and 8 coating films of the comparative photosensitive resin composition (1). Except for one sheet, the entire surface was exposed with a high-pressure mercury lamp using a manual exposure machine. Regarding the photosensitive resin composition, 8 sheets were prepared, and the entire surface exposure was performed at 0, 10, 40, 60, 80, 100, 120, and 150 mJ / cm ² . Regarding the comparative photosensitive resin composition, seven sheets were prepared, and the whole surface exposure was performed at 0, 40, 60, 80, 100, 120, and 200 mJ / cm ² , respectively. The remaining one sheet was exposed in a pattern. Thereafter, each coating film was heated at 155 ° C. for 10 minutes.

(Evaluation of remaining film rate)
Each of the coating films prepared using the photosensitive resin composition (1) and the comparative photosensitive resin composition (1) and exposed to the whole surface was prepared by using a 9: 1 solution of tetramethylammonium hydroxide 2.38 wt% and isopropanol. The coating film using the photosensitive resin composition (1) and the comparative photosensitive resin composition (1) was immersed for 40 minutes in the mixed solution at room temperature, and the remaining film thickness on the glass was measured. The results are shown in FIG. In the figure, the normalized residual film ratio was defined as film thickness after development × 100 / maximum film thickness after development.

Since the residual film rate increased with the increase in the amount of UV irradiation, it was shown that the base generator generated a base by UV irradiation and heating, and imidization proceeded. The photosensitive resin composition (1) of the present invention has a normalized film thickness of about 1 at 80 mJ / cm ² , whereas the comparative photosensitive resin composition (1) has a normalized film thickness of 120 mJ / cm ^2. It became about 1. In the photosensitive resin composition of the present invention, it was revealed that imidization proceeds with a small exposure amount as compared with the comparative photosensitive resin composition, and it was shown that the sensitivity was high. The photosensitive resin composition (1) of the present invention was found to proceed with imidization with a particularly small exposure amount.

About the coating film exposed to the pattern shape created using the photosensitive resin composition (1), it was immersed in the solution which mixed tetramethylammonium hydroxide 2.38weight% aqueous solution and isopropanol 9: 1. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, it was heated at 350 ° C. for 1 hour to perform imidization. From this result, it became clear that the photosensitive resin composition of the present invention can form a good pattern. The photosensitive resin composition (1) of the present invention formed a pattern at 150 mJ / cm ² . On the other hand, when the comparative photosensitive resin composition (1) was tested in the same manner, a pattern was finally formed at 250 mJ / cm ² .

(Examples 5 to 7: Preparation of photosensitive resin compositions (5) to (7))
Using the base generators (5) to (7) according to the present invention, photosensitive resin compositions (5) to (7) having the following compositions were prepared.
Epoxy resin (YP50EK35 (phenoxy resin), 35% by weight methyl ethyl ketone solution manufactured by Nippon Steel Chemical Co., Ltd.): 100 parts by weight Each base generator: 10 parts by weight

Each of the photosensitive resin compositions (5) to (7) was spin-coated on glass so as to have a final film thickness of 0.5 μm, and dried on a hot plate at 80 ° C. for 15 minutes. Two coating films were obtained. About 1 sheet of the coating film of the photosensitive resin composition, 100 J / cm < ² > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Thereafter, each coating film was heated at 150 ° C. for 60 minutes. When the heated coating film was immersed in a mixed solution of isopropanol and chloroform (isopropanol: chloroform = 4: 1 (volume ratio)) at room temperature for 10 minutes, the heated coating film after the exposure did not dissolve in the mixed solution, but was epoxy. It became clear that the resin was cured. On the other hand, the coating film heated without exposure was dissolved in the mixed solution.

(Example 8: Preparation of photosensitive resin composition (8))
Photosensitivity comprising 100 parts by weight of hexamethylene diisocyanate (manufactured by Kanto Chemical) as the isocyanate resin, 150 parts by weight of polytetrahydrofuran (manufactured by Aldrich) as the resin having a hydroxyl group, 10 parts by weight of the base generator (1), and 500 parts by weight of tetrahydrofuran. Resin composition (8) was prepared.

The photosensitive resin composition (8) was spin-coated on chrome-plated glass so that the final film thickness was 0.5 μm, and dried on a hot plate at 60 ° C. for 5 minutes. One coating film was obtained. The obtained coating film was 100 J / cm ² whole surface exposed with a high pressure mercury lamp using a manual exposure machine. Then, when it heated at 120 degreeC for 10 minute (s) and cooled to room temperature, the low-elasticity solid substance was obtained and it confirmed that hardening with an isocyanate group and a hydroxyl group advanced.

(Example 9: Preparation of photosensitive resin composition (9))
After mixing 100 parts by weight of the alkoxysilane condensate (1) obtained in Synthesis Example 2 above and 10 parts by weight of the base generator (1), the mixture is dissolved in 500 parts by weight of tetrahydrofuran as a solvent to obtain a photosensitive resin composition. A product (9) was prepared.

The photosensitive resin composition (9) was spin-coated on two chrome-plated glasses so that the final film thickness was 0.5 μm, respectively, and dried on an 80 ° C. hot plate for 5 minutes. Two coating films of the conductive resin composition were obtained. About 1 sheet of the coating film of the photosensitive resin composition, 100 J / cm < ² > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Thereafter, each of the exposed coating film and the unexposed coating film was heated at 120 ° C. for 30 minutes. Infrared absorption spectrum measurement was performed on each sample before and after heating. As a result, for the sample after heating of the exposed coating film, a peak of 1020 cm ^-1 attributed to the Si-O-Si bond indicating polymerization appeared, and it was attributed to Si-OCH ₃ indicating the raw material. The peaks at 2850 cm ^-1 and 850 cm ^-1 were reduced compared to the sample before heating. In the sample after heating the unexposed film, a peak of 1020 cm ^-1 attributed to the Si-O-Si bond, indicating that it was polymerized, appeared. It was small. From these, it has been clarified that, when the photobase generator of the present invention is used for exposure, a base is generated and the polymerization of the alkoxysilane condensate is promoted.

Claims (13)

A base generator, which is represented by the following chemical formula (1) and generates a base by irradiation and heating of electromagnetic waves.

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R ¹ and R ² is an organic group, and R ³ and R ⁴ are each independently hydrogen, halogen, Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, which are the same be different even good ^{.R 5, R 6,} R ⁷ and ^{R 8} are each independently hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, two Nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group, may be different even in the same, R ^5, R ⁶ , any one of R ⁷ and R ⁸ has a cycloalkoxy group or a tertiary alkoxy group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are two or more of them. It may be bonded to form a cyclic structure and may contain a heteroatom bond, and R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves. ) The base generator according to claim 1, wherein R ⁶ and / or R ^{7 in} formula (1) has a cycloalkoxy group and / or a tertiary alkoxy group which may have a substituent. .   The base generator according to claim 1 or 2, wherein the cycloalkoxy group is a monocyclic or polycyclic cycloalkoxy group containing a 5-membered ring, a 6-membered ring, and / or a 7-membered ring. .   The base generator according to any one of claims 1 to 3, wherein the cycloalkoxy group has 5 to 20 carbon atoms.   The base generator according to any one of claims 1 to 4, wherein the tertiary alkoxy group has 4 to 20 carbon atoms.   A polymer precursor whose reaction to the final product is promoted by heating with a basic substance or in the presence of a basic substance, and the base generator according to any one of claims 1 to 5. A photosensitive resin composition characterized by containing.   The polymer precursor is selected from the group consisting of a compound and polymer having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzoxazole precursor. The photosensitive resin composition according to claim 6, comprising the above.   The photosensitive resin composition according to claim 6, wherein the polymer precursor is soluble in a basic solution.   The photosensitive resin composition according to claim 6, wherein the polymer precursor is a polyimide precursor or a polybenzoxazole precursor.   Any one of Claims 6 to 9 used as a material for forming paints, printing inks, sealants, or adhesives, or display devices, semiconductor devices, electronic components, microelectromechanical systems, optically shaped objects, optical members, or building materials. A photosensitive resin composition according to claim 1.   The pattern formation material which consists of the photosensitive resin composition as described in any one of Claims 6 thru | or 10.   A coating film or a molded body is formed using the photosensitive resin composition according to any one of claims 6 to 10, and the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern, after irradiation. Alternatively, a method for producing a relief pattern is characterized in that development is carried out after heating at the same time as irradiation to change the solubility of the irradiated portion.   Printed matter, paint, sealant, adhesive, display device, semiconductor device, electronic component, at least part of which is formed of the photosensitive resin composition according to any one of claims 6 to 10 or a cured product thereof. An article of any one of a micro electro mechanical system, an optically shaped object, an optical member, and a building material.

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