JP2012092328A - Base generator, photosensitive resin composition, pattern formation material comprising the photosensitive resin composition, and method for producing relief pattern and article using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base generator with less occurrence of outgas or odor when in use, and to provide a photosensitive resin composition applicable to various polymeric precursors and having less occurrence of outgas or odor when in use.SOLUTION: The base generator which generates a base by electromagnetic irradiation is characterized by including in one molecule, at least one blocked covalent bond-forming group in which a part of the structure thereof varies by heating and/or electromagnetic irradiation to become a functional group possible to form a covalent bond together with other molecules. The photosensitive resin composition includes the polymeric precursor in which the reaction to a final product is accelerated by a basic material or heating in the presence of the basic material, and contains the base generator as an essential component.

Description

  TECHNICAL FIELD The present invention relates to a photosensitive resin composition using a base generator and a base generator that generates a base upon irradiation and heating of electromagnetic waves, and in particular, a product or member formed through a patterning step using electromagnetic waves or a curing accelerating step. The present invention relates to a photosensitive resin composition that can be suitably used as a material, a pattern forming material comprising the photosensitive resin composition, a method for producing a relief pattern, and an article produced using the resin composition. is there.

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 that polyimide has, 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, etc. 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 Reference 6. Patent Documents 7 and 8 disclose photosensitive resin compositions using carbamate-type photobase generators. Further, Patent Documents 9 and 10 disclose photosensitive resin compositions using an oxime type photobase generator.

  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, in the conventional photobase generator as described above, after the base is generated, the dissociated light absorption site remains as an independent low-molecular compound in the resin film or the molded body. The occurrence of this is a concern.

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 2006-189591 A JP 2008-247747 A JP 2007-249013 A JP 2008-003581 A

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

  The present invention has been made in view of the above circumstances, and its main purpose is to generate a photobase generator that can be applied to various polymer precursors with little generation of outgas and odor during use, and a photosensitive resin. It is to provide a composition.

  The base generator according to the present invention is a base generator that generates a base by irradiation with electromagnetic waves, and a part of the structure can be changed by heating and / or irradiation with electromagnetic waves to form a covalent bond with another molecule. It is characterized by having one or more blocked covalent bond forming groups to be functional groups in one molecule.

  The base generator according to the present invention forms a blocked covalent bond that becomes a functional group (covalent bond-forming group) capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves. By having one or more groups in one molecule, the base generators react with each other or with a functional group capable of reacting with the covalent bond-forming group present in the system by heating and / or irradiation with electromagnetic waves. . For this reason, after heating and / or electromagnetic wave irradiation, it is fixed in the system or has a high molecular weight in the system, so that outgas and odor are less generated during use. And before heating and / or electromagnetic wave irradiation, since the covalent bond forming group is blocked, there is an advantage that storage stability is excellent and solubility is improved.

  In the base generator according to the present invention, the functional group capable of forming a covalent bond with the other molecule (covalent bond forming group) is an isocyanato group, a thioisocyanato group, a hydroxyl group, a carboxyl group, or an amino group. It is preferable from the viewpoint that reactivity is increased and outgas and odor are less likely to occur during use.

  The base generator according to the present invention is preferably a base generator represented by the following chemical formula (1-1), the following chemical formula (1-2), or the following chemical formula (1-3).

（式（１−１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は有機基であり、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、水素原子、ハロゲン原子、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、水素原子、ハロゲン原子、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い。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。但し、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。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 (1-1), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. R ¹ and R ² are bonded to each other. May 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. Atom, halogen atom, 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 There may be different even in the same ^{.R 5, R 6,} R ⁷ and ^{R 8} each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, shea Nord 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, which may be the same or different R ⁵ , R ⁶ , R ^7, and R ⁸ may be bonded to each other to form a cyclic structure, and may include a hetero atom bond, provided that R ³ , A block in which at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a functional group capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves. R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

（式（１−２）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は有機基であり、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。Ｒ¹⁰及びＲ^10’はそれぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、ニトロ基、シリル基、シラノール基、又は有機基である。Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、水素原子、ハロゲン原子、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い。Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５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。但し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。）

(In Formula (1-2), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. R ¹ and R ² are bonded to each other. may form a cyclic structure Te, may contain a binding heteroatom. proviso that at least one of R ¹ and R ² is an organic group .R ¹⁰ and R ^{10 'are} each independently hydrogen An atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, and R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ are each independently a hydrogen atom or a halogen atom; , 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, amino group An ammonio group or an organic group, may be different even in the same ^{.R 11, R 12, R 13} , R 14 and ^{R 15,} to form a cyclic structure two or more of them are combined However, at least one of R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ may be partially changed by heating and / or irradiation with electromagnetic waves. And has a blocked covalent bond forming group that becomes a functional group capable of forming a covalent bond with another molecule.)

（式（１−３）中、Ｒ^１７は、有機基で置換されたアミノ基又は有機基、Ｒ^１８及びＲ^１９は、それぞれ独立に、水素原子、ハロゲン原子、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いが、Ｒ^１８及びＲ^１９の少なくとも１つはヘテロ原子を有していても良い芳香族化合物である。Ｒ^１７、Ｒ^１８及びＲ^１９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^１８及びＲ^１９の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。）

(In Formula (1-3), R ¹⁷ is an amino group or an organic group substituted with an organic group, and R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a halogen atom, a sulfide group, a silyl group, or a 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, which may be the same or different , R ¹⁸ and R ¹⁹ are each an aromatic compound optionally having a hetero atom, and two or more of R ¹⁷ , R ¹⁸ and R ¹⁹ are combined to form a cyclic structure. even if well, at least one good .R ¹⁸ and R ¹⁹ may contain a binding heteroatom, heating and / or electromagnetic waves other molecules co portion of the structure is changed by irradiation of Having a functional group capable of forming a bond blocking covalent bonding group.)

In the base generator according to the present invention, the blocked covalent bond forming group preferably includes at least one structure selected from the group consisting of the following (i) to (iv).
(I) a structure in which the hydrogen atom at the terminal of the hydroxyl group is substituted with one or more selected from the group consisting of organic groups represented by the following formulas (2-1) to (2-6);
(Ii) One or more selected from the group consisting of an organic group represented by the following formula (2-1), an organic group represented by the following formula (2-3), and an organic group in which the terminal hydrogen atom of the carboxyl group Structure replaced with
(Iii) a structure in which one hydrogen atom at the terminal of the amino group is substituted with an organic group represented by the following formula (2-2), and (iv) the following formula (3-1) to the following formula (3-6) One or more structures selected from the group consisting of substituents represented by:

（式（２−１）中、Ｒ^３０、Ｒ^３１、Ｒ^３２はそれぞれ独立に水素原子、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原子、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 a hydrogen atom, a halogen atom or an organic group, R ³³ is an organic group, and R ³⁰ , R ³¹ , R ³² , R ³³ may be bonded to each other to represent a cyclic structure, and in formula (2-2), R ³⁴ is an organic group, and in formula (2-3), R ³⁵ , R ³⁶ , R ³⁷ 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 is an organic group.)

（式（３−１）中、Ｑは酸素原子又は硫黄原子であり、Ｒ^４２は有機基である。式（３−２）中、Ｅｗはそれぞれ独立に電子吸引性基であり、Ｑは酸素原子又は硫黄原子である。式（３−３）中、Ｑは酸素原子又は硫黄原子であり、Ｒ^４３及びＲ^４４はそれぞれ独立に水素原子又は有機基である。式（３−４）中、Ｑは酸素原子又は硫黄原子であり、ｎは３〜７である。）

(In Formula (3-1), Q is an oxygen atom or a sulfur atom, R ⁴² is an organic group. In Formula (3-2), Ew is each independently an electron-withdrawing group, and Q is oxygen. In formula (3-3), Q is an oxygen atom or sulfur atom, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an organic group, in formula (3-4), Q is an oxygen atom or a sulfur atom, and n is 3-7.)

  The photosensitive resin composition according to the present invention is a photosensitive resin composition comprising a polymer precursor whose reaction to the final product is accelerated by heating with a basic substance or in the presence of a basic substance. The base generator according to the present invention is contained as an essential component.

  In the photosensitive resin composition according to the present invention, the polymer precursor forms a covalent bond with a functional group (covalent bond forming group) capable of forming a covalent bond with the other molecule of the base generator. It is preferable to have a functional group capable of In such a case, since the base generator or its residue is bonded and fixed to the polymer precursor by heating and / or irradiation with electromagnetic waves, the generation of outgas and odor is more easily suppressed during use. .

  In the photosensitive resin composition according to the present invention, the polymer precursor is a compound and polymer having an epoxy group, an isocyanato group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzo. It is preferably at least one selected from the group consisting of oxazole precursors.

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.

  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.

According to the present invention, it is possible to provide a photobase generator that can be applied to various polymer precursors with less outgassing and odor generation during use.
The photosensitive resin composition according to the present invention generates less outgas and odor during use because the absorption group of the base generator is bonded to and fixed to the polymer precursor after heating and / or electromagnetic wave irradiation. .

The present invention will be described in detail below.
In the present invention, (meth) acryloyl means acryloyl and / or methacryloyl, (meth) acryl means acryl and / or methacryl, and (meth) acrylate means acrylate and / or methacrylate. means.
Moreover, in this invention, an organic group represents the general term of the functional group containing at least 1 carbon atom.
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>
A base generator for generating a base upon irradiation with electromagnetic waves according to the present invention, which is a functional group capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves It is characterized by having one or more chemical covalent bond forming groups in one molecule.

  A base generator that generates a base by irradiation with electromagnetic waves is usually a low molecular compound in which the base is dissociated by heating and / or irradiation with electromagnetic waves, and the sites other than the base derived from the base generator are independent in the system. Since it remained, there was a concern about the occurrence of outgas and odor during use. If it remains as an independent low molecular weight compound, it will volatilize during use during light irradiation and post-baking to generate outgas and odor, re-solidify after volatilization and adhere to manufacturing equipment and products, or do not volatilize. There is a risk of remaining in the final product and causing problems such as loss of heat resistance and stability of the product.

In that respect, the base generator according to the present invention is blocked as a functional group (covalent bond-forming group) capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or electromagnetic wave irradiation. By having one or more covalent bond forming groups in one molecule, by heating and / or irradiation with electromagnetic waves, the base generators or functional groups capable of reacting with the covalent bond forming groups present in the system react. For this reason, after heating and / or electromagnetic wave irradiation, it is fixed in the system or has a high molecular weight in the system, so that outgas and odor are less generated during use. Furthermore, since the covalent bond-forming group is blocked before heating and / or electromagnetic wave irradiation, there are merits of excellent storage stability and improved solubility.
In addition, the amount of degradation product derived from the base generator that re-solidifies after volatilization and adheres to the manufacturing apparatus or product, or the amount of degradation product derived from the base generation agent that elutes in the developer or cleaning solution is significantly reduced. Furthermore, the amount of the low molecular compound derived from the base generator remaining after curing is reduced, and the heat resistance and stability of the final product are improved.

The base generator according to the present invention generates a base when irradiated with electromagnetic waves, and the structure is not particularly limited as long as it is a structure capable of introducing a blocked covalent bond forming group.
The base generator according to the present invention is a low-molecular compound that easily volatilizes from the point that the effect of suppressing outgassing and odor generation during use by having the covalent bond-forming group is more effective. It is mentioned as a suitable thing. For example, the base generator according to the present invention is preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably 1000 or less, but is not limited thereto.

  The base generator according to the present invention is preferably a base generator containing no salt in the structure, and preferably has no charge on the nitrogen atom of the base moiety generated in the base generator. In the base generator according to the present invention, it is preferable that the generated base is latentized using a covalent bond, and the base generation mechanism is shared between the nitrogen atom of the generated base portion and the adjacent atom. It is preferable that the bond is broken to generate a base. When the base generator does not contain a salt in the structure, the base generator can be neutralized, so that the solvent solubility is good and the pot life is improved. Further, there is an advantage that compatibility with components used in combination such as a polymer precursor is often good.

As the base generator according to the present invention, it is preferable that the generated base is latentized using a covalent bond as described above, and the generated base is latentized using an amide bond, carbamate bond, or oxime bond. It is preferable.
Examples of the base generator according to the present invention include a base generator having a cinnamic amide structure as disclosed in Patent Documents 5 and 6, and a carbamate structure as disclosed in Patent Documents 7 and 8 above. Examples include base generators, oxime structures as disclosed in Patent Documents 9 and 10 above, base generators having a carbamoyl oxime structure, etc., but are not limited thereto, and other known base generator structures are also included. Can be used.

In the base generator according to the present invention, a blocked covalent bond forming group that becomes a functional group capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves is contained in one molecule. One or more are included.
Here, “a part of the structure changes” includes an aspect in which a part of the structure of the original substituent is changed by the removal of the protecting group (blocking agent) and / or the transfer reaction or the like. It is done. “Blocking” means that a functional group is temporarily reacted with another compound to reduce the reactive activity of the functional group, and the functional group is changed by heating and / or irradiation with electromagnetic waves until a part of the structure is changed. The state in which the reaction activity cannot be used. In the “blocking” mode, in addition to the case where the functional group to be finally used is temporarily reacted with another compound, the function to be finally used as in the example of the formula (3-6) described later is used. This includes a case where a functional group different from the group is temporarily reacted with another compound and then used as a functional group to be finally used with a transfer reaction.
The “covalent bond forming group” refers to a functional group that can react with other functional groups to form a covalent bond. In the present invention, the “functional group capable of forming a covalent bond with another molecule” potentially introduced into the base generator may be simply referred to as a covalent bond-forming group.

Examples of the covalent bond-forming group that is potentially introduced after being blocked include an isocyanato group, a thioisocyanato group, a hydroxyl group, a carboxyl group, an amino group, and an alkynyl group.
In the base generator of the present invention, an amino group (—NH ₂ ) can be used as a covalent bond-forming group that is potentially introduced. For example, when heated before light irradiation, a part of the structure changes to become an amino group, which reacts with a functional group capable of reacting with the amino group under the heating condition to immobilize the base generator in the system. Then, after light irradiation, a base is generated and the base is used.

The covalent bond-forming group potentially introduced into the base generator may be appropriately selected depending on the combination of the functional group capable of reacting with the covalent bond-forming group present in the same composition as the base generator. .
For example, when an isocyanato group, an isothiocyanato group, a carboxyl group, an epoxy group, an oxetane group, or a thiirane group is present in the same composition, the covalent bond-forming group potentially introduced into the base generator may be a hydroxyl group. Or an amino group.

In addition, when an isocyanato group, a thioisocyanato group, a hydroxyl group, or an amino group is present in the same composition, the covalent bond-forming group that is potentially introduced into the base generator includes an isocyanato group or a thioisocyanato group. .
Further, when a hydroxyl group, an amino group, an epoxy group, a thiirane group, or an oxetane group is present in the same composition, the covalent bond-forming group potentially introduced into the base generator includes a carboxyl group. .
Moreover, when an azide group exists in the same composition, an alkynyl group is mentioned as a covalent bond forming group potentially introduced into a base generator.

  In the base generator according to the present invention, the number of blocked covalent bond forming groups in one molecule may be appropriately selected according to the situation in which the base generator is used. For example, when a compound such as a polymer precursor having a functional group that reacts with a potentially introduced covalent bond-forming group is present in the system used, the blocked covalent bond-forming group is 1 If there is one in the molecule, it is fixed in the system. On the other hand, the base generator according to the present invention has two or more blocked covalent bond-forming groups in one molecule, and in the two or more blocked covalent bond-forming groups, there are covalent bond-forming groups that react with each other. If introduced potentially, the base generators undergo a cross-linking reaction to increase the molecular weight and are less likely to be volatilized out of the system. In addition, even when the base generator according to the present invention has one blocked covalent bond-forming group in one molecule, it forms a covalent bond that reacts with each other alone or in combination of two or more in the system. If the group is potentially introduced, the base generators undergo a cross-linking reaction to dimerize and are less likely to be volatilized out of the system.

As an aspect in which the base generator according to the present invention is used, the base generator is fixed to the polymer precursor using a polymer precursor having a functional group that reacts with the covalent bond-forming group of the base generator. Embodiments are most preferred.
In addition, using a polymer precursor that does not have a functional group that reacts with a covalent bond-forming group, the molecule has two or more blocked covalent bond-forming groups in one molecule, and the two or more blocked covalent bond-forming groups Also preferred is an embodiment in which covalent bond forming groups that react with each other are potentially introduced and the base generators undergo a crosslinking reaction to increase the molecular weight.
Furthermore, using a polymer precursor that does not have a functional group that reacts with a covalent bond-forming group, it has one blocked covalent bond-forming group per molecule, and dimerization occurs when base generators react with each other. It is also possible to use this mode.

  As a substituent that is partially changed in structure by heating and / or irradiation with an electromagnetic wave to become a hydroxyl group, carboxyl group, or amino group, a known hydroxyl group, carboxyl group, or amino group blocking reaction is used. Obtainable.

  As a substituent that is partially changed in structure by heating and / or irradiation with an electromagnetic wave to become a hydroxyl group, a hydrogen atom at the terminal of the hydroxyl group is represented by the following formula (2-1) to the following formula (2-6). Having a structure substituted with one or more selected from the group consisting of groups is preferred from the viewpoint of easy synthesis.

Moreover, as a substituent which a part of structure changes by heating and / or electromagnetic wave irradiation and becomes a carboxyl group, the hydrogen atom at the terminal of the carboxyl group is an organic group represented by the above formula (2-1), the following formula It is preferable from the viewpoint of easy synthesis that it has a structure substituted with one or more selected from the group consisting of an organic group represented by (2-3) and an organic group. The structure in which the hydrogen atom at the terminal of the carboxyl group is substituted with an organic group is an ester group (—COOR ⁴¹ ; where R ⁴¹ is an organic group). Especially, it is preferable from a point with easy synthesis | combination that the hydrogen atom of the terminal of a carboxyl group has the structure substituted by the organic group represented by a following formula (2-1) or the following formula (2-3).

Examples of the substituent group in which a part of the structure by the irradiation of heat and / or electromagnetic waves is changed to an amino group (-NH ^2), 1 single hydrogen atom of the terminal amino group (-NH ²⁾ is the following formula ( The structure substituted with the organic group represented by 2-2) is preferable from the viewpoint of easy synthesis.

（式（２−１）中、Ｒ^３０、Ｒ^３１、Ｒ^３２はそれぞれ独立に水素原子、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原子、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 a hydrogen atom, a halogen atom or an organic group, R ³³ is an organic group, and R ³⁰ , R ³¹ , R ³² , R ³³ may be bonded to each other to represent a cyclic structure, and in formula (2-2), R ³⁴ is an organic group, and in formula (2-3), R ³⁵ , R ³⁶ , R ³⁷ 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 is an organic group.)

The organic group represented by the above formula (2-1) can be obtained by a reaction between a hydroxyl group or a carboxyl group and a vinyl ether compound.
In formula (2-1), R ³⁰ , R ³¹ , and R ³² are preferably a hydrogen atom, 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 or an amino group and a so-called carbonate-based protective group.
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 or a carboxyl group and 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.
Formula is not particularly limited as R ⁴⁰ in (2-6), for example, it is mentioned a benzyl group.

A structure in which the hydrogen at the terminal of the carboxyl group is substituted with an organic group, and an ester group (—COOR ⁴¹ ; where R ⁴¹ is an organic group) is obtained by reaction of the carboxyl group and the hydroxyl group using the Williamson reaction. be able to.
No particular limitation is imposed on the R ⁴¹ of the above ester groups, for example, a methyl group, an alkyl group such as a tert- butyl group, an aryl group such as a phenyl group, aralkyl groups such as benzyl group is preferably used.

In addition, as a substituent that is partially converted into an isocyanato group or a thioisocyanato group by heating and / or irradiation with electromagnetic waves, a reaction for blocking a known isocyanato group or a reaction for forming an isocyanato group by transfer. It can be obtained using it.
Substituents whose structure is partially changed by heating and / or electromagnetic wave irradiation to become isocyanato groups or thioisocyanato groups are composed of substituents represented by the following formulas (3-1) to (3-6). One or more structures selected from the group are preferably included from the viewpoint of easy synthesis. Substituents represented by the following formulas (3-1) to (3-6) are dissociated or transferred by heating and / or irradiation with electromagnetic waves to become isocyanato groups or thioisocyanato groups.

（式（３−１）中、Ｑは酸素原子又は硫黄原子であり、Ｒ^４２は有機基である。式（３−２）中、Ｅｗはそれぞれ独立に電子吸引性基であり、Ｑは酸素原子又は硫黄原子である。式（３−３）中、Ｑは酸素原子又は硫黄原子であり、Ｒ^４３及びＲ^４４はそれぞれ独立に水素原子又は有機基である。式（３−４）中、Ｑは酸素原子又は硫黄原子であり、ｎは３〜７である。）

(In Formula (3-1), Q is an oxygen atom or a sulfur atom, R ⁴² is an organic group. In Formula (3-2), Ew is each independently an electron-withdrawing group, and Q is oxygen. In formula (3-3), Q is an oxygen atom or sulfur atom, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an organic group, in formula (3-4), Q is an oxygen atom or a sulfur atom, and n is 3-7.)

The substituent represented by the above formula (3-1) can be obtained by reacting an isocyanato group or a thioisocyanato group with a hydroxyl group-containing compound such as alcohol or phenol.
No particular limitation is imposed on the R ⁴² of formula (3-1), for example, a methyl group, an alkyl group such as a tert- butyl group, an aryl group such as a phenyl group, aralkyl groups such as benzyl group is preferably used.

The substituent represented by the above formula (3-2) can be obtained by reacting an isocyanato group or a thioisocyanato group with a compound having an active methylene group. Here, the active methylene group means a methylene group (—CH ₂ —) having reaction activity, and means a methylene group sandwiched between two electron-withdrawing groups. Examples of the electron withdrawing group include a carbonyl group, a cyano group, a nitro group, a sulfonyl group, a sulfinyl group, and a phosphono group.
Examples of the compound having an active methylene group include malonate esters such as dimethyl malonate and diethyl malonate, acetoacetate esters such as methyl acetoacetate and ethyl acetoacetate, acetylacetone, malononitrile, ethyl cyanoacetate, ethyl nitroacetate, p -Ethyl trissulfonyl acetate, ethyl phenylsulfinyl acetate, trimethyl phosphonoacetate and the like can be used. Of these, malonic acid ester and acetoacetic acid ester are preferable from the viewpoint of reactivity.

Ew in the formula (3-2) is a residue in the compound having an active methylene group, and is not particularly limited. For example, an ester group (—COOR), an acyl group (—COR), a cyano group (—CN), a nitro group (—NO ₂ ), a sulfonyl group (—S (═O) ₂ R), a sulfinyl group (—S ( ═O) R), a phospho group (—P (═O) (OR) ₂ )) and the like (where R is an organic group).

The substituent represented by the above formula (3-3) is an isocyanato group or a thioisocyanato group, and formal oxime, acetal oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2-butanone oxime, or diethylglyoxime It can obtain by reaction with oximes.
R ⁴³ and R ^{44 in} the formula (3-3) are not particularly limited. For example, alkyl groups such as a methyl group and a tert-butyl group, aryl groups such as a phenyl group, and aralkyl groups such as a benzyl group are preferable. Used.

  The substituent represented by the above formula (3-4) can be obtained by reacting an isocyanato group or a thioisocyanato group with a lactam such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam.

  The substituent represented by the above formula (3-5) can be obtained by dimerizing an isocyanato group using a catalyst and carbodiimidizing as shown in the following formula. The substituent represented by the above formula (3-5) is dissociated by heating to generate an isocyanato group. In the present invention, a base generator having an isocyanato group at the terminal is prepared, and the base generator can be obtained by dimerization using a catalyst. Here, as the catalyst, for example, any known phosphorus catalyst is preferably used. For example, 1-phenyl-2-phosphorin-1-oxide, 3-methyl-2-phosphorin-1-oxide, 1-ethyl- Examples include 2-phosphorin-1-oxide, 3-methyl-1-phenyl-2-phosphorin-1-oxide, and phospholine oxides such as these 3-phosphorin isomers.

（式中、Ｒは有機基である。）

(In the formula, R is an organic group.)

  The substituent represented by the above formula (3-6) can be obtained by reacting the carboxyl group with an acid azide such as diphenyl phosphate azide. The substituent represented by the above formula (3-6) undergoes a Curtius transition by heating to generate an isocyanato group. In this invention, it can obtain by preparing the base generator which has a carboxyl group at the terminal, and reacting acid azides, such as diphenylphosphoric acid azide, with the carboxyl group of the said base generator.

Moreover, as a substituent which a part of structure changes by heating and / or electromagnetic wave irradiation, and becomes an alkynyl group, it can obtain using the reaction which blocks a well-known alkynyl group.
Examples of the reaction for blocking an alkynyl group include a reaction for blocking with a silyl group represented by the above formula (2-3).

  The base generator according to the present invention is a base generator represented by the following chemical formula (1-1), the following chemical formula (1-2) or the following chemical formula (1-3), depending on the basic substance or the base. It is preferable because it can be used for various polymer precursors whose reaction to the final product is promoted by heating in the presence of the active substance. Among them, it is a base generator represented by the following chemical formula (1-1) because it has excellent sensitivity and can obtain a pattern having a good shape regardless of the type of the polymer precursor. preferable.

（式（１−１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は有機基であり、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、水素原子、ハロゲン原子、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、水素原子、ハロゲン原子、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い。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。但し、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。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 (1-1), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. R ¹ and R ² are bonded to each other. May 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. Atom, halogen atom, 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 There may be different even in the same ^{.R 5, R 6,} R ⁷ and ^{R 8} each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, shea Nord 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, which may be the same or different R ⁵ , R ⁶ , R ^7, and R ⁸ may be bonded to each other to form a cyclic structure, and may include a hetero atom bond, provided that R ³ , A block in which at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a functional group capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves. R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

（式（１−２）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は有機基であり、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。Ｒ¹⁰及びＲ^10’はそれぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、ニトロ基、シリル基、シラノール基、又は有機基である。Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、水素原子、ハロゲン原子、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い。Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５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。但し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。）

(In Formula (1-2), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. R ¹ and R ² are bonded to each other. may form a cyclic structure Te, may contain a binding heteroatom. proviso that at least one of R ¹ and R ² is an organic group .R ¹⁰ and R ^{10 'are} each independently hydrogen An atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, and R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ are each independently a hydrogen atom or a halogen atom; , 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, amino group An ammonio group or an organic group, may be different even in the same ^{.R 11, R 12, R 13} , R 14 and ^{R 15,} to form a cyclic structure two or more of them are combined However, at least one of R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ may be partially changed by heating and / or irradiation with electromagnetic waves. And has a blocked covalent bond forming group that becomes a functional group capable of forming a covalent bond with another molecule.)

（式（１−３）中、Ｒ^１７は、有機基で置換されたアミノ基又は有機基、Ｒ^１８及びＲ^１９は、それぞれ独立に、水素原子、ハロゲン原子、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いが、Ｒ^１８及びＲ^１９の少なくとも１つはヘテロ原子を有していても良い芳香族化合物である。Ｒ^１７、Ｒ^１８及びＲ^１９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^１８及びＲ^１９の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。）

(In Formula (1-3), R ¹⁷ is an amino group or an organic group substituted with an organic group, and R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a halogen atom, a sulfide group, a silyl group, or a 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, which may be the same or different , R ¹⁸ and R ¹⁹ are each an aromatic compound optionally having a hetero atom, and two or more of R ¹⁷ , R ¹⁸ and R ¹⁹ are combined to form a cyclic structure. even if well, at least one good .R ¹⁸ and R ¹⁹ may contain a binding heteroatom, heating and / or electromagnetic waves other molecules co portion of the structure is changed by irradiation of Having a functional group capable of forming a bond blocking covalent bonding group.)

When the base generator represented by the chemical formula (1-1) is irradiated with an electromagnetic wave, as shown by the following formula, (—CR ⁴ = CR ³ —C) in the formula (1-1) The (= O)-) moiety isomerizes from the trans form to the cis form. Further, when R ⁹ is a protecting group by heating and / or irradiation with electromagnetic waves, the protecting group R ⁹ is deprotected and cyclized to produce a base (NHR ¹ R ² ). In the base generator represented by the chemical formula (1-1), the hydroxyl group at the ortho position of the carbon-carbon double bond is used for intramolecular cyclization for base generation. Therefore, in addition to the structure in which the hydroxyl group at the ortho position is protected by a protecting group, the group having the blocked covalent bond-forming group of the present invention is provided.

Moreover, when the base generator represented by the chemical formula (1-2) is irradiated with an electromagnetic wave, the bond is cleaved by a photodecarboxylation reaction of a carbamate bond to generate a base (NHR ¹ R ² ).
Furthermore, the base generator represented by the above chemical formula (1-3) is an oxime ester derivative, which undergoes an intramolecular cleavage reaction by absorption of electromagnetic waves according to the following reaction formula to generate amine or hydrazine.

In the base generator represented by the chemical formula (1-1), chemical formula (1-2), or chemical formula (1-3), the blocked covalent bond-forming group is R ³ or R in the chemical formula (1-1). ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ^{15 in} the chemical formula (1-2), the chemical formula (1- It may be contained in at least one of R ¹⁸ and R ^{19 in} 3). The blocked covalent bond-forming group may be directly bonded to the carbon atom at any of the above substitution positions, but may be bonded to the carbon atom through an appropriate linking group.

For example, two or more of R ^{5 to} R ^{8 in} the chemical formula (1-1), R ^{11 to} R ^{15 in} the chemical formula (1-2), and R ^{17 to} R ^{19 in} the chemical formula (1-3) When bonded to form an alicyclic hydrocarbon structure such as a cyclohexyl group, or two or more bonded and share the atoms of the benzene ring to which they are bonded, naphthalene, anthracene, phenanthrene, indene When a condensed ring such as fluorene is formed, it may have a blocked covalent bond forming group as a substituent of the cyclic structure.

  The linking group used for bonding the blocked covalent bond-forming group to the carbon atom at any substitution position is not particularly limited, and examples thereof include straight chain, branched or cyclic hydrocarbon groups, ether bonds, and thioether bonds. , Carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (—N═C (—R) —, —C (═NR) —, where R is a hydrogen atom or an organic group), carbonate Examples include a bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and a combination thereof.

In the above chemical formula (1-1) and chemical formula (1-2), 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. is there. Further, NHR ¹ R ² is a base, but R ¹ and R ² are each preferably an organic group not containing an amino group. 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 a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic.
The organic group is preferably a linear, branched or cyclic hydrocarbon group which may contain a substituent, may contain an unsaturated bond, and may contain a heteroatom bond.
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 an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond Etc. 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)-: where R is a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond.

Substituents other than the hydrocarbon group in the organic group of R ¹ and R ² , that is, substituents included in the organic group, which are different from the hydrocarbon group, and may be substituted with a hydrocarbon group. The substituent is not particularly limited as long as the effect of the present invention is not impaired, and is not limited to a halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl Group, silanol 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 -Tel group, saturated or unsaturated alkyl thioether group, aryl ether group, aryl thioether group, amino group (-NH2, -NHR, -NRR ': where R and R' are each independently a hydrocarbon group), etc. Can be mentioned. The hydrogen atom 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, 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 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 basic substance to be generated is NHR ¹ R ² , a primary amine, a secondary amine, or a heterocyclic compound is exemplified. 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} produced is not only a basic substance such as a monoamine having only one NH group capable of forming an amide bond, but also 2 NH groups capable of forming an amide bond such as diamine, triamine and tetraamine. It may be a basic substance having two or more. In the case where the generated NHR ¹ R ² is a basic substance having two or more NH groups, for example, an amide bond can be formed at one or more terminals of R ¹ and / or R ^{2 in} the formula (1-1). Examples include a structure in which a photolatent moiety that generates a base having an NH group by irradiation with electromagnetic waves and heating is further bonded. As the photolatent site, to one or more ends of the ^{R 1} and / or ^{R 2} in the formula (1-1), except for ^{R 1} and / or ^{R 2} of formula (1-1) residues Are further bonded to each other.

  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 an organic group), and examples thereof include imidazole, purine, triazole, and derivatives thereof.

As amines higher than diamine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, Linear aliphatic alkylenediamines such as 1,9-nonanediamine and 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-1,4-butanediamine, 2,3- Branched aliphatic alkylenediamine such as dimethyl-1,4-butanediamine; diethylenetriamine, triethylenetetramine, tetraethylenepentami Polyethylene amines represented by the general formula _{NH 2 (CH 2 CH 2 NH} ) n H and the like; cyclohexane diamine, methylcyclohexane diamine, isophorone diamine, norbornane dimethylamine, tricyclodecane dimethylamine, alicyclic such as menthenediamine Diamine; aromatic diamine such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, diaminodiphenylsulfone; benzenetriamine, melamine, 2,4, Examples include triamines such as 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 thermophysical properties and basicity of the basic substance to be generated 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 substance 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.

Further, when the base generated in the present invention is a secondary amine and / or a heterocyclic compound, it is preferable from the viewpoint of increasing the 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 leaving base 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 (1-1), R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, A sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group, which may be the same or different. R ³ and R ⁴ may have a blocked covalent bond forming group.
R ³ and R ⁴ are each preferably a hydrogen atom from the viewpoint of easily achieving high sensitivity.

In the present invention, in particular, when at least one of R ³ and R ^{4 in} the chemical formula (1-1) is not a hydrogen atom but the specific functional group, both R ³ and R ⁴ are hydrogen. Compared to the case of atoms, the base generator of the present invention can further improve the solubility in an organic solvent and improve the affinity with a 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 atom such as fluorine, the affinity with a polymer precursor containing a halogen atom 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 combined with a desired organic solvent or polymer precursor, and a substituent is appropriately introduced, so that the solubility in the desired organic solvent and the desired polymer precursor can be reduced. It is possible to improve the affinity.

The halogen atom and the organic group are not particularly limited as long as the effects of the present invention are not impaired, and those similar to those listed for R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described later can be used.
The organic group in R ³ and R ⁴ is usually a monovalent organic group.

When R ³ and R ⁴ have 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; a C 4 to 23 carbon atom such as a cyclopentyl group or a cyclohexyl group. A cycloalkyl group; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group (-ROAr group); Aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; Alkyl group having 2 to 21 carbon atoms having cyano group such as cyanomethyl group and β-cyanoethyl group; Hydroxymethyl group An alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as an alkoxy group having 1 to 20 carbon atoms such as a methoxy group or an ethoxy group, Toamido group, benzenesulfonyl cyanamide group _{(C 6 H 5 SO 2 NH} 2 -) amide group having a carbon number of 2 to 21, such as a methylthio group, an alkylthio group having 1 to 20 carbon atoms such as an ethylthio group (-SR group) , An acyl group having 1 to 20 carbon atoms such as acetyl group and benzoyl group, an ester group having 2 to 21 carbon atoms such as methoxycarbonyl group and acetoxy group (-COOR group and -OCOR group), phenyl group, naphthyl group, biphenyl An aryl group having 6 to 20 carbon atoms such as a group or tolyl group, an aryl group having 6 to 20 carbon atoms substituted by an electron donating group and / or an electron withdrawing group, an electron donating group and / or an electron withdrawing group. A substituted benzyl group, a cyano group, and a methylthio group (—SCH ₃ ) are preferred. The alkyl moiety may be linear, branched or cyclic.

In the chemical formula (1-2), R ¹⁰ and R ^{10 ′} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group. For example, the same as those mentioned in R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described later can be used.

R ^{5 to} R ⁸ in the chemical formula (1-1) and R ^{11 to} R ¹⁵ in the chemical formula (1-2) are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, or a 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 group, It may be different. Two or more of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a cyclic structure, or may include a hetero atom bond. In the chemical formula (1-1), it is preferable that at least one of R ^{5 to} R ⁸ has a blocked covalent bond forming group.

It is preferable to introduce one or more substituents into R ^{5 to} R ⁸ in the chemical formula (1-1) and R ^{11 to} R ¹⁵ in the chemical formula (1-2). In particular, in the case of the base generator represented by the above chemical formula (1-1), the double bond between the α carbon and β carbon located at the α-position and β-position of the carbonyl bond is an isomerization reaction from a trans isomer to a cis isomer. There are several factors that promote the efficiency of the reaction, for example, the size of the steric hindrance around the carbon-carbon double bond, the electronic state of the conjugated chain extending around the carbon-carbon double bond, and the like. By introducing at least one substituent as described above into R ^{5 to} R ⁸ , the conjugated chain around the carbon-carbon double bond is expanded, and the base generation sensitivity can be improved. In R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , the wavelength of light to be absorbed can be adjusted by introducing at least one substituent as described above, and the substituent is introduced. It is also possible to absorb the desired wavelength. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. It is also possible to improve the solubility and compatibility with the polymer precursor to be combined. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.
When R ^{5 to} R ⁸ in the chemical formula (1-1) and R ^{11 to} R ^{15 in} the chemical formula (1-2) have a blocked covalent bond forming group, these objects can be sufficiently achieved. In some cases, it may have other substituents as appropriate.

  As a guideline of what substituents should be introduced to shift the absorption wavelength with respect to a desired wavelength, the Interspection of the Ultraviolet Products (AI Scott 1964) and the spectrum of organic compounds The table described in the identification method 5th edition (RM Silverstein 1993) can be referred to. By referring to these, it is possible to know a measure of how long the maximum absorption wavelength of the compound is increased.

R ¹¹ or R ^{15 in} the chemical formula (1-2) is preferably a nitro group from the viewpoint of improving the sensitivity of the base generator represented by the chemical formula (1-2).

In R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , examples of the halogen atom include fluorine, chlorine, bromine and the like.
In R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , 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. Etc. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic. As the bond other than the hydrocarbon group in the organic groups of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , the same bond as the bond other than the hydrocarbon group of R ¹ and R ² can be used. ^The organic group of R 5 to R ⁸ and ^R 11 ^{to R 15} may be bonded to the benzene ring via a bond other than a hydrocarbon group. Further, in the organic groups of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ , substituents other than hydrocarbon groups (substituents included in the organic groups are substituted with substituents different from hydrocarbon groups, and hydrocarbon groups). As the substituent which may be present, the same substituents as those other than the hydrocarbon groups of R ¹ and R ² can be used.
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, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, 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.
The organic group in R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ is usually a monovalent organic group, but may form a divalent or higher organic group when forming a cyclic structure to be described later.

Two or more of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ 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. For example, each of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ is bonded to two or more of them, and an atom of a benzene ring to which each of R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ is bonded. It may be shared to form a condensed ring such as naphthalene, anthracene, phenanthrene or indene.

R ^{5 to} R ⁸ or R ^{11 to} R ¹⁵ are hydrogen atom, halogen atom, 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, methyl group, ethyl group, propyl group and other alkyl groups having 1 to 20 carbon atoms; cyclopentyl group, cyclohexyl group and the like having 4 to 23 carbon atoms An alkyl group; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and a tolyl group; An aralkyl group having 7 to 20 carbon atoms such as a sulfur group; a phenoxymethyl group, a 2-phenoxyethyl group Aryloxyalkyl groups having 7 to 26 carbon atoms such as 4-phenoxybutyl group (-ROAr group); alkyl groups having 2 to 21 carbon atoms having a cyano group such as cyanomethyl group and β-cyanoethyl group; An alkyl group having 1 to 20 carbon atoms having a hydroxyl group; an alkyl ether group optionally substituted with an aryl group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, and a benzyloxy group; a phenoxy group and a naphthyloxy group An arylthio group such as a methylthio group or an ethylthio group (an —SR group); an arylthioether group such as a benzylthio group or a naphthylthio group; an acetamide group or a benzenesulfonamide group (C ₆ H - ₅ SO ₂ NH ₂₎ amide group having a carbon number of 2 to 21 such as, acetyl groups, a 1 to 20 carbon atoms such as a benzoyl group Thioacyl group; acylthio group such as acetylthio group and benzoylthio group; ester group having 2 to 21 carbon atoms such as methoxycarbonyl group, acetoxy group and benzyloxycarbonyl group (—COOR group and —OCOR group), and A C6-C20 aryl group substituted with an electron-donating group and / or an electron-withdrawing group, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, a cyano group; a carbamoyl group; a carbamoyloxy group; A cyanooxy group (cyanato group); a cyanothio group (thiocyanato group); and a formyl group are preferable. The alkyl moiety may be linear, branched or cyclic.
^As the R 5 to R ⁸ or ^R 11 ^{to R 15,} and two or more of them are ^combined, share the atoms of the benzene ring of R 5 to R ⁸ or ^R 11 ^{to R 15} are bonded A condensed ring such as naphthalene, anthracene, phenanthrene, and indene is also preferable from the viewpoint of increasing the absorption wavelength.

In Formula (1-1), 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 a hydrogen atom, 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. To do. 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, a 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 is 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 (1-1) does not decompose in the base generator used in the present invention. If it is, it will not be specifically limited but 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 present in the formula (1-1) to be one or more selected from the group consisting of organic groups represented by the above formula (2-1) to the following formula (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 amide group does not decompose.

  The structure represented by the chemical formula (1-1) 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%.

In the chemical formula (1-3), R ¹⁷ is an amino group or an organic group substituted with an organic group. In the case where R ¹⁷ is an organic group, the same as those listed for R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ can be used.
When R ^{17 in the} chemical formula (1-3) is an amino group substituted with an organic group, it has a carbamoyloxime structure represented by the following formula (1-3 ′). Can generate hydrazine.

（式（１−３’）中、Ｒ^１８及びＲ^１９は、化学式（１−３）と同じであり、Ｒ^２０及びＲ^２１は、上記化学式（１−１）のＲ^１及びＲ^２と同じである。Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１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^１８及びＲ^１９の少なくとも１つが、加熱及び／又は電磁波の照射により構造の一部が変化して他の分子と共有結合を形成可能な官能基となるブロック化共有結合形成基を有する。）

(In the formula (1-3 ′), R ¹⁸ and R ¹⁹ are the same as those in the chemical formula (1-3), and R ²⁰ and R ²¹ are the same as R ¹ and R ^{2 in} the chemical formula (1-1). it ^{.R 18,} R ^{19, R 20} and ^{R 21,} those two or more together, may form a cyclic structure which may contain a binding heteroatom ^{.R 18} and R ^At least one of ¹⁹ has a blocked covalent bond-forming group that becomes a functional group capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves.

In the above chemical formulas (1-3) and (1-3 ′), at least one of R ¹⁸ and R ^{19 is} an aromatic compound which may have a hetero atom. The state in which at least one of R ¹⁸ and R ¹⁹ is substituted with an aromatic compound refers to a state in which the aromatic compound is directly covalently bonded to the carbon to which R ¹⁸ and R ¹⁹ are bonded. To tell. Here, the aromatic compound refers to a cyclic unsaturated organic compound, and includes aromatic hydrocarbons and aromatic heterocyclic compounds. Examples of the aromatic compound include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorene group, an anthranyl group, a phenanthrenyl group, and a pyrenyl group, as well as a furanyl group, a thiophenyl group, and a pyrrolyl group. And heteroaromatic compounds such as (thio) xanthenyl group, (thio) xanthonyl group, coumaryl group, anthraquinolyl group, and the like. The substituent which these may have may be the same as R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described above. When one of R ¹⁸ and R ¹⁹ is an organic group other than an aromatic compound, it may be the same as R ^{5 to} R ⁸ and R ^{11 to} R ¹⁵ described above.

In the above chemical formulas (1-3) and (1-3 ′), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ may be bonded to each other to form a cyclic structure. It may also contain a heteroatom bond. Examples of the case where R ¹⁸ and R ¹⁹ are bonded to form a cyclic structure include an embodiment in which a fluorene ring is formed together with the carbon to which R ¹⁸ and R ¹⁹ are bonded. Further, when R ¹⁸ and R ¹⁷ or R ¹⁸ and R ²⁰ are bonded to form a cyclic structure, for example, R ¹⁸ and R ¹⁷ , R ¹⁸ and R ²⁰ are an aliphatic hydrocarbon group and / or The aspect connected with the aromatic hydrocarbon group is mentioned.

  Examples of the base generator of the present invention are shown below, but are not limited thereto. The substitution position and the type of base are not limited to these, and can be appropriately changed.

The base generator according to the present invention preferably has a temperature (5% weight loss temperature) when heated to 5% by weight from the initial weight is 40 ° C. or higher, more preferably 60 ° C. or higher. Is preferable, and it is more preferable that it is 100 degreeC or more. 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 x% weight reduction temperature is the time when the weight of the sample is reduced by x% from the initial weight when the weight loss is measured using a thermogravimetric analyzer (ie, the sample weight is the initial (100−x )%)).

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 (1-1) can be synthesized with reference to, for example, Patent Document 6 and Japanese Patent Application No. 2010-176384 by the present inventors. In the base generator represented by the above chemical formula (1-1), 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. . Moreover, the base generator represented by the chemical formula (1-2) can be synthesized with reference to Patent Documents 7 and 8, for example. Moreover, the base generator represented by the chemical formula (1-3) can be synthesized with reference to, for example, the above-mentioned Patent Documents 9 and 10.

The formation of a blocked covalent bond forming group and the introduction of a 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.
For example, when a hydrogen atom at the terminal of a hydroxyl group or a carboxyl group is substituted with an organic group represented by the above formula (2-1), for example, in the presence of an acid catalyst such as pyridinium paratoluenesulfonate, the hydroxyl group or carboxyl group Can be obtained by dissolving dimethylformamide with a base generator in which is introduced and a vinyl ether compound and stirring them.
Moreover, when substituting the hydrogen atom of the terminal of a hydroxyl group or an amino group, and the organic group represented by said Formula (2-2), the base generator into which the hydroxyl group and the amino group were introduce | transduced, and a carbonate type protective group It can be synthesized with an introduction reagent (for example, di-t-butyl dicarbonate, benzyloxycarbonyl chloride, N- (9-fluorenylmethoxycarbonyloxy) succinimide, etc.).
When substituting the hydrogen atom at the terminal of the hydroxyl group or carboxyl group with the organic group represented by the above formula (2-3), a base having a hydroxyl group or carboxyl group introduced in dimethylformamide under a base catalyst such as imidazole It can be synthesized by a generator and a reagent for introducing a silyl ether protecting group (for example, chlorotrimethylsilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, etc.).

When substituting the hydrogen atom at the terminal of the hydroxyl group and the organic group represented by the above formula (2-4), the base generator and the acid chloride or acid anhydride into which the hydroxyl group has been introduced under a base catalyst such as triethylamine Can be synthesized.
When substituting the hydrogen atom at the terminal of the hydroxyl group with the organic group represented by the above formula (2-5), a base generator in which a hydroxyl group is introduced and ether-based protection in the presence of a strong base such as sodium hydride It can be synthesized by a group (halide, such as benzyl chloride).
When substituting the hydrogen atom at the terminal of the hydroxyl group and the organic group represented by the above formula (2-6), synthesis is performed with a base generator having a hydroxyl group introduced and a carbamate-based protecting group (isocyanate such as benzyl isocyanate). it can.
Moreover, in order to esterify a carboxyl group, it is compoundable by making alcohol or phenol act in presence of a condensing agent.

In addition, when a carboxyl group is introduced, for example, a cinnamic acid derivative is formed using an aldehyde introduced with a carboxyl group protected with a silyl ether-based protecting group as a raw material, and an amide bond is formed, followed by deprotection. it can.
In addition, when introducing an isocyanato group, a compound having a carboxyl group as a substituent is reacted with diphenyl phosphate azide and the like, a substituent containing a carboxylic acid azide is introduced, an amide bond is formed, and then heated. The isocyanato group may be obtained by performing the Curtius transition.
Also, an isocyanate group can be introduced by introducing a primary amine as a substituent and reacting with phosgene or triphosgene.
When a thiocyanate group is introduced, a thiocyanate group can be introduced by introducing a halogen atom as a substituent and allowing the thiocyanate such as sodium thiocyanate or potassium thiocyanate to act on the halogen atom.

In order to introduce the substituent represented by the above formula (3-1), an isocyanato group or a thioisocyanato group and a hydroxyl group-containing compound such as alcohol or phenol are used as a catalyst with an organometallic salt such as tin, zinc, or lead. It can be obtained by reacting with.
The substituent represented by the above formula (3-2) includes an isocyanato group or a thioisocyanato group and a compound having an active methylene group such as dimethyl malonate or ethyl acetoacetate having an active methylene group, tin, zinc, lead It can obtain by making it react using organometallic salts etc. as a catalyst.
The substituent represented by the above formula (3-3) can be obtained by reacting an isocyanato group or a thioisocyanato group with an oxime using an organometallic salt such as tin, zinc, or lead as a catalyst.

The substituent represented by the above formula (3-4) can be obtained by reacting an isocyanato group or a thioisocyanato group with a lactam using an organometallic salt such as tin, zinc, or lead as a catalyst.
The substituent represented by the above formula (3-5) is obtained by dimerizing an isocyanato group and carbodiimidizing it using a phospholine-based catalyst such as phospholine, phosphoridine, or phospholine oxide as shown in the following formula. be able to.
The substituent represented by the above formula (3-6) can be obtained by introducing a carboxyl group and reacting an acid azide such as diphenyl phosphate azide.

  When the base generator of the present invention functions as a photobase generator, the polymer precursor absorbs at least a part of the exposure wavelength in order to sufficiently exhibit the base generation function for becoming 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 used in the present invention absorbs electromagnetic waves having at least one wavelength among electromagnetic waves having wavelengths of at least 365 nm, 405 nm, and 436 nm. In such a case, it is preferable because the number of applicable polymer precursors is further increased.

  When the base generator of the present invention functions as a photobase generator, the molar extinction coefficient is 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at 405 nm. It is preferable from the viewpoint of further increase.

In addition, the base generator of the present invention has absorption in the wavelength region means that the base generator of the present invention is added to a solvent that does not absorb in the wavelength region (for example, acetonitrile) at 1 × 10 ⁻⁴ mol / Dissolved at a concentration of L or less (usually about 1 × 10 ⁻⁴ mol / L to about 1 × 10 ⁻⁵ mol / L. It may be appropriately adjusted so as to obtain an appropriate absorption intensity), and ultraviolet visible It can be clarified by measuring the absorbance with a spectrophotometer (for example, UV-2550, manufactured by Shimadzu Corporation).

  The base generator of the present invention is suitably used as a base generator for preparing a photosensitive resin composition in combination with a polymer precursor described later.

In addition, the base generator of the present invention has two or more blocked covalent bond forming groups per site other than the base that dissociates after base generation, and the two or more blocked covalent bond formations. If a covalent bond-forming group that reacts with each other is potentially introduced into the group, it also functions as a polymer precursor and can be used as a base-generating polymer precursor.
Therefore, in such a case, even if a polymer precursor that promotes the reaction to the final product by heating in the presence of the basic substance described later or in the presence of the basic substance is not included, the present invention can be used. A base-generating polymer precursor is an essential component and can be used as a polymer precursor composition or a photosensitive resin composition. The polymer precursor composition or the photosensitive resin composition may be an embodiment in which the base-generating polymer precursor of the present invention is contained in an amount of 100% by weight based on the total solid content of the composition. If necessary, the polymer precursor composition or photosensitive resin composition includes a compound containing a functional group capable of reacting with a potentially introduced covalent bond-forming group, other photosensitive components, and sensitization. Other components such as an agent, a base proliferating agent, and a solvent may be included.
When the base generator of the present invention is used as a base-generating polymer precursor, among them, the base to be generated is a polyvalent amine such as diamine, and the base capable of dissociating the blocked covalent bond forming group after base generation It is preferable to have two or more per site other than the above, and a case where a covalent bond-forming group that reacts with each other is potentially introduced into the two or more blocked covalent bond-forming groups.

<Photosensitive resin composition>
The photosensitive resin composition according to the present invention is a photosensitive resin composition comprising a polymer precursor whose reaction to the final product is accelerated by heating with a basic substance or in the presence of a basic substance. The base generator according to the present invention is contained as an essential component.

In the photosensitive resin composition of the present invention, the base generator has one or more blocked covalent bond-forming groups in one molecule, so that the base generators are heated together and / or irradiated with electromagnetic waves, It reacts with a functional group capable of reacting with the covalent bond forming group present in the system. For this reason, after heating and / or electromagnetic wave irradiation, it is fixed in the system or has a high molecular weight in the system, so that outgas and odor are less generated during use. And before heating and / or electromagnetic wave irradiation, the covalent bond forming group potentially introduced into the base generator is blocked, so that it has excellent storage stability and improved solubility. There is.
In addition, the amount of degradation product derived from the base generator that re-solidifies after volatilization and adheres to the manufacturing apparatus or product, or the amount of degradation product derived from the base generation agent that elutes in the developer or cleaning solution is significantly reduced. Furthermore, the amount of the low molecular compound derived from the base generator remaining after curing is reduced, and the heat resistance and stability of the final product are improved.

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. As described above, when the base generator contained as an essential component is a base generator that can be used as a base-generating polymer precursor, it is heated by a basic substance or by the presence of a basic substance. Even if a polymer precursor that promotes the reaction to the final product is not separately contained in addition to the base generator, a photosensitive resin composition can be obtained.
The polymer precursor used in the photosensitive resin composition according to the present invention preferably has a functional group capable of forming a covalent bond with a covalent bond forming group of the base generator. In such a case, since the base generator or its residue is bonded and fixed to the polymer precursor by heating and / or irradiation with electromagnetic waves, the generation of outgas and odor is more easily suppressed during use. .

  The polymer precursor used in the photosensitive resin composition according to the present invention includes compounds and polymers having an epoxy group, an isocyanato group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzoxazole. It is preferable to include one or more selected from the group consisting of precursors. These polymer precursors have a functional group capable of forming a covalent bond with the covalent bond-forming group of the base generator, or form a covalent bond with the covalent bond-forming group of the base generator. It is usually used in combination with a compound having a functional group that can easily introduce a functional group that can be formed or that can form a covalent bond with a covalent bond-forming group of the base generator.

  For example, when the polymer precursor is a polymer precursor having any one or more of isocyanato group, isothiocyanato group, carboxyl group, epoxy group, oxetane group, and thiirane group, the base generator is potentially The covalent bond forming group to be introduced is preferably at least one of a hydroxyl group and an amino group.

  In addition, when the polymer precursor is a polymer precursor having any one or more of an isocyanato group, a thioisocyanato group, a hydroxyl group, or an amino group, a covalent bond forming group that is potentially introduced into the base generator Is preferably at least one of an isocyanato group and a thioisocyanato group.

In addition, when the polymer precursor is a polymer precursor having any one or more of an amino group, an epoxy group, a thiirane group, or an oxetane group, covalent bond formation that is potentially introduced into the base generator The group is preferably a carboxyl group.
Although the typical example of a polymer precursor is given to the following, it 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 isocyanato 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). Group, enoxy group, amino group, aminoxy group, amide group, and hydrolyzable group selected from the group consisting of halogen atoms).

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) Roxypolyether with epoxy groups at both ends; YP series, etc.), Denatite series manufactured by Nagase ChemteX, Denacol series, Epolite series manufactured by Kyoeisha Chemical Co., Epiol series manufactured by NOF Corporation, Examples include, but are not limited to, the Marproof series. 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 undergoes a cross-linking reaction between molecules include a combination of a compound having two or more isocyanato 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 isocyanato 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 isocyanato groups in the molecule and a compound having two or more hydroxyl groups in the molecule, and a compound having two or more isocyanato groups in the molecule Examples include a combination of polymers (polyols) having two or more hydroxyl groups in the molecule.

(Compounds and polymers having isocyanato groups)
As the compound and polymer having an isocyanato group, known compounds can be used without particular limitation as long as they have two or more isocyanato groups in the molecule. Such compounds include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl). -In addition to low molecular weight compounds typified by cyclohexane, 4,4-dicyclohexylmethane diisocyanate, etc., polymers having an isocyanate group in the side chain or terminal of an oligomer or polymer having a weight average molecular weight of 3,000 or more may be used. Good. Examples of polyisocyanates derived from these diisocyanates include isocyanurate type polyisocyanates, burette type polyisocyanates, and urethane type polyisocyanates.

(Compounds having a hydroxyl group and polymers)
The compound and polymer having an isocyanato 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. Examples of the compound having a high molecular weight hydroxyl group include polyether polyols such as polyethylene glycol, poly (1,2-propanediol), and polytetramethylene ether glycol, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

(Polysiloxane precursor)
Examples of the compound that undergoes hydrolysis and polycondensation between molecules include polysiloxane precursors. As the polysiloxane precursor in the present invention, it is preferable to introduce a hydroxyl group, an amino group, an isocyanato group, an isothiocyanato group, an epoxy group, an oxetane group, or a thiirane group.
As the polysiloxane precursor, Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, a phenyl group, or a hydrogen atom, which may have a substituent, Represents 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 atom, and n is an integer from 0 to 3. ) And hydrolyzed polycondensates of the organosilicon compounds. Among these, those in which n is 0 to 2 in the above formula are preferable. Further, from the viewpoint that the silica-dispersed oligomer solution is easily prepared and easily available, the hydrolyzable group is preferably an alkoxy group.
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.
In addition, since the polyimide precursor may have an amino group or an acid anhydride group at the terminal, the polymer precursor having the amino group, the polymer precursor having an acid anhydride group, or the polymer precursor having a hydroxyl group. Can be used as a body. The polybenzoxazole precursor can be used as the above-described polymer precursor having an amino group or a polymer precursor having a hydroxyl group.
As the polyimide precursor and polybenzoxazole precursor in the present invention, it is preferable to introduce a hydroxyl group, an amino group, an isocyanato group, an isothiocyanato group, an epoxy group, an oxetane group, or a thiirane group.

(Polyimide precursor)
As the polyimide precursor, a polyamic acid having a repeating unit represented by the following chemical formula (4) is preferably used.

（式（４）中、Ｒ^５１は４価の有機基である。Ｒ^５２は２価の有機基である。Ｒ^５３及びＲ^５４は、水素原子、又は有機基である。ｎは１以上の自然数である。）

(In Formula (4), R ⁵¹ is a tetravalent organic group. R ⁵² is a divalent organic group. R ⁵³ and R ⁵⁴ are a hydrogen atom or an organic group. N is 1 or more. It is a natural number.)

Examples of the case where R ⁵³ and R ⁵⁴ are organic groups are represented by an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _n H _2n OC _m H _{2m + 1} containing an ether bond therein. The structure etc. can be mentioned.

  As the polyimide precursor, a polyamic acid represented by the following formula (4 ') is preferably used from the viewpoint of alkali developability.

（式（４’）中、Ｒ^５１は４価の有機基である。Ｒ^５２は２価の有機基である。ｎは１以上の自然数である。）

(In Formula (4 ′), R ⁵¹ is a tetravalent organic group. R ⁵² is a divalent organic group. N is a natural number of 1 or more.)

In formulas (4) and (4 ′), the tetravalent R ⁵¹ represents a tetracarboxylic acid residue derived from an acid dianhydride or the like, and the divalent R ⁵² represents a diamine residue. Incidentally, tetravalent R ⁵¹ represents only valence for bonding with the acid, but may have further substituents other. Similarly, the divalent value of R ⁵² 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 formula (4 ′), R ⁵¹ or R ⁵² is preferably an aromatic compound, and R ⁵¹ and R ⁵² are more preferably aromatic compounds. At this time, in R ⁵¹ of the chemical formula (4 ′), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ⁵¹ may be bonded to the same aromatic ring. It may be bonded to different aromatic rings. Similarly, in R ⁵² of the chemical formula (4 ′), two groups ((—NH—) ₂ ) bonded to R ⁵² may be bonded to the same aromatic ring, or may be bonded to different aromatic rings. It may be combined.

  Further, the polyamic acid represented by the chemical formula (4 ′) may be composed of a single repeating unit or may be composed of two or more kinds of 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.

  Further, depending on the purpose, any one or two or more of ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanato group, and isopropenyl group serving as a crosslinking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

  The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient. Rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like can be mentioned.

  In addition, diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring, for example, There exists what is represented by following formula (5). Specific examples include benzidine and the like.

（化学式（５）中、ａは１以上の自然数、アミノ基はベンゼン環同士の結合に対して、メタ位または、パラ位に結合する。）

(In the chemical formula (5), 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 benzene rings.)

Furthermore, in the above formula (5), a diamine having a substituent at a position where the amino group on the benzene ring is not substituted and which does not participate in the bond with another benzene ring can also be used. These substituents are organic groups, but they may be bonded to each other.
Specific examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino. Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl and the like can be mentioned.

  When the finally obtained polyimide is used as an optical waveguide or an optical circuit component, the transmittance for electromagnetic waves having a wavelength of 1 μm or less can be improved by introducing fluorine as a substituent of the aromatic ring.

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

On the other hand, in order to synthesize a polyimide precursor, for example, while cooling a solution in which 4,4′-diaminodiphenyl ether as an amine component is dissolved in an organic polar solvent such as N-methylpyrrolidone, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is gradually added and stirred to obtain a polyimide precursor solution.
The polyimide precursor synthesized in this way has a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide obtained is required to have heat resistance and dimensional stability. Is preferred. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure The proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and particularly preferably wholly aromatic polyimide.

<Polybenzoxazole precursor>
As the polybenzoxazole precursor used in the present invention, a polyamide alcohol having a repeating unit represented by the following chemical formula (6) 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.

（化学式（６）中、Ｒ^５５は２価の有機基である。Ｒ^５６は４価の有機基である。ｎは１以上の自然数である。）

(In the chemical formula (6), R ⁵⁵ is a divalent organic group. R ⁵⁶ is a tetravalent organic group. N is a natural number of 1 or more.)

The divalent value of R ⁵⁵ indicates only the valence for bonding with an acid, but may further have a further substituent. Similarly, the tetravalent value of R ⁵⁶ 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 (6) gives excellent heat resistance and dimensional stability to the finally obtained polybenzoxazole. In the chemical formula (6), R ⁵⁵ or R ⁵⁶ is preferably an aromatic compound, and R ⁵⁵ and RR ⁵⁶ are more preferably aromatic compounds. At this time, in R ⁵⁵ of the chemical formula (6), two groups (—CO—) ₂ bonded to R ⁵⁵ may be bonded to the same aromatic ring or bonded to different aromatic rings. May be. Similarly, in R ⁵⁶ of the chemical formula (6), four groups ((—NH—) ₂ (—OH) ₂ ) bonded to R ⁵⁶ may be bonded to the same aromatic ring, It may be bonded to different aromatic rings.

  The polyamide alcohol represented by the chemical formula (6) 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. Obtainable.

  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.

  Polyamic acid and polybenzoxazole precursors are reduced in solubility by the reaction to the final product due to the action of the basic substance, and therefore combined with a decrease in solubility due to base generation of the base generator. The photosensitive resin composition of the present invention has the advantage that the solubility contrast between the exposed area and the unexposed area can be further increased.

<Other ingredients>
The photosensitive resin composition according to the present invention may be a simple mixture of the base generator, one or more kinds of polymer precursors, and a solvent, and further includes a light or thermosetting component, a polymer. A photosensitive resin composition may be prepared by blending a non-polymerizable binder resin other than the precursor and other components. Moreover, you may add the other photosensitive component which generate | occur | produces an acid or a base with light as an auxiliary | assistant role of the base generator of this invention. Further, a base proliferating agent that generates a base by decomposition or rearrangement reaction by the action of a small amount of base generated from the base generator may be used in combination, or a sensitizer may be added.

  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 benzyl dimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like Monoacylphosphine oxides or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones.

  Examples of the compound that generates an acid by light include a photosensitive diazoquinone compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. US Pat. Nos. 2,772,972, 2,797, No. 213, No. 3,669,658. In addition, known photoacid generators such as triazine and derivatives thereof, sulfonic acid oxime ester compounds, sulfonic acid iodonium salts, and sulfonic acid sulfonium salts can be used. Examples of the compound that generates a base by light include 2,6-dimethyl-3,5-dicyano-4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl. Examples include -4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. it can.

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.

The 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 transmits the polymer and to improve the 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 addition, various organic or inorganic low-molecular or high-molecular compounds may be blended to impart processing characteristics and various functionalities to the resin composition according to the present invention. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

The base generator according to the present invention can be contained in the range of 0.1 to 100% by weight with respect to the entire solid content of the photosensitive resin composition. As described above, when the base generator of the present invention is used as a base-generating polymer precursor, it may be 100% by weight based on the total solid content of the composition.
When used as a curing agent, the base generator according to the present invention is usually 0.1 to 80% by weight, preferably based on the entire solid content of the photosensitive resin composition, although it depends on the degree of curing. It is contained within the range of 0.5 to 60% by weight. If it is less than 0.1% by weight, the solubility contrast between the exposed and unexposed parts may not be sufficiently increased, and if it exceeds 80% by weight, the properties of the final cured resin will be reflected in the final product. It is hard to be done.
On the other hand, when the base generator according to the present invention is used as a curing accelerator, it can be cured with a small amount of addition, and is usually 0.1 to 30 weights with respect to the entire solid content of the photosensitive resin composition. %, Preferably 0.5 to 20% by weight.
In the photosensitive resin composition according to the present invention, when a polymer precursor different from the base generator is used, the polymer precursor (solid content) is obtained from the film physical properties of the obtained pattern, particularly film strength and heat resistance. From the point, it is preferable to contain 0.1 to 99.9 weight% and 0.5 to 70 weight% with respect to the whole solid content of the photosensitive resin composition. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a monomer that is liquid at room temperature.

  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 is the same as the photosensitive resin composition according to the present invention in printing ink, paint, sealing agent, adhesive, electronic material, optical circuit component, molding material, resist material, building material, light. It can be used for all known fields and products in which resin materials are used, such as modeling and optical members. 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 optically shaped object, 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. Moreover, 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.

  Further, in the present invention, printed matter, paint, sealant, adhesive, display device, semiconductor device, electronic component, microscopic part, which is at least partly formed of the photosensitive resin composition according to the present invention or its thermoset. Articles of either electromechanical systems, stereolithography, optical members or building materials are provided.

<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.

  In the method for producing a relief pattern, the surface of the coating film or molded body made of the photosensitive resin composition is protected from the developer by using the polymer precursor in combination with the base generator according to the present invention. Therefore, it is possible to form a pattern for development without using a resist film.

  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. The base generator according to the present invention generates a basic substance only in the exposed part by irradiating the film with electromagnetic waves and heating after irradiation or simultaneously with irradiation. The basic substance acts as a catalyst that promotes the reaction of the polymer precursor in the exposed area to the final product.

When using a polymer precursor whose thermosetting temperature is lowered by the catalytic action of a base, such as a polyimide precursor or a polybenzoxazole precursor, first, such a polymer precursor and a base according to the present invention are used. The part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the generator 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 concerning this invention 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 irradiated with electromagnetic waves through a mask having a predetermined pattern, and is exposed to a pattern. After heating, the unexposed portion of the film is developed and removed with an appropriate developer to obtain a desired pattern. A patterned film can be obtained.

  The exposure method and 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.

  When deprotection of a protecting group or generation of a covalent bond forming group is performed only by electromagnetic wave irradiation, deprotection or covalent bond forming group generation may be performed by an electromagnetic wave irradiated to generate a base, or deprotection or covalent bond formation may be performed. The wavelength may be changed between an electromagnetic wave for generating a group and an electromagnetic wave for generating a base. For example, deprotection or generation of a covalent bond-forming group is performed by irradiating a long wavelength electromagnetic wave, followed by isomerization for generating a base with a short wavelength electromagnetic wave. The irradiation amount of the electromagnetic wave in these cases varies depending on the electromagnetic wave and is not particularly limited, and is appropriately adjusted.

The polymer to be combined is heated before or after exposure or simultaneously with exposure to generate a base by deprotecting the protecting group or changing a part of the structure to generate a covalent bond-forming group. It is appropriately selected depending on the precursor and 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. Moreover, in order to prevent decomposition | disassembly other than base generation | occurrence | production of the base generator concerning this invention, it is preferable to heat at 400 degrees C or less, and it is preferable to heat at 300 degrees C or less.
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.
In addition, you may heat before exposure and may perform deprotection and a covalent bond formation group production | generation. Depending on the type of the protecting group or the like, the sensitivity of the base generator may be deteriorated by introducing a protecting group or the like to shorten the absorption wavelength. In such a case, the sensitivity at the time of electromagnetic wave irradiation can be improved by deprotecting a protective group or the like in advance by heating before the electromagnetic wave irradiation and irradiating the electromagnetic wave.
It should be noted that the deprotection of the protecting group and the conditions for generating a covalent bond-forming group can vary depending on the components that coexist in the composition. For example, when other photoacid generators or photobase generators are included, the heating temperature after exposure may change due to the influence of an acid / base generated by light irradiation.
The heating for protecting group deprotection before the electromagnetic wave irradiation may be a coating film drying process or another heating process. In this case, as the heating temperature, a temperature capable of deprotection may be selected as appropriate, but it is preferably 50 ° C. to 180 ° C., and the time is preferably 10 seconds to 60 minutes.
In addition, when heating is performed, the protecting group may be deprotected at a low temperature to generate a base at a higher temperature.

In addition, deprotection of the protecting group in R ⁹ of the above formula (1-1) and generation of a covalent bond forming group by changing a part of the structure are performed only by heating or only by electromagnetic wave irradiation. Also good.
Further, deprotection or covalent bond forming group generation may be performed by performing heating and electromagnetic wave irradiation simultaneously or alternately with heating and electromagnetic wave irradiation.

  The base generator represented by the formula (1-1) 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 formula (1-1), the base is formed by heating after electromagnetic wave irradiation (exposure) or simultaneously with electromagnetic wave irradiation. appear. Exposure and heating may be performed alternately. The most efficient method is a method of heating simultaneously with exposure.

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 and unexposed areas 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 and methyl isobutyl ketone, other tetrahydrofuran, chloroform, acetonitrile and the like alone or Two or more types may be added in combination. 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 structure of the produced base generator was confirmed by ¹ H NMR.
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
Heating of the coating film: As One Co., Ltd., HOT PLATE EC-1200 (may be described as a hot plate in this example)

(Production Example 1: Synthesis of base generator (1))
In a 300 mL three-necked flask, 5.0 g (27.8 mmol) of 2,4-dihydroxy-cinnamic acid (manufactured by Sigma Aldrich Japan) was dissolved in 100 mL of tetrahydrofuran, and 1-ethyl-3- (3-dimethyl) was dissolved. Aminopropyl) carbodiimide hydrochloride (EDC) (Tokyo Chemical Industry Co., Ltd.) 6.4g (33.3 mmol) was added. After 30 minutes, 3.3 ml (33.3 mmol) of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After completion of the reaction, the reaction mixture was dissolved in water, extracted with chloroform, and then washed with saturated aqueous sodium hydrogen carbonate solution, 1N hydrochloric acid and saturated brine. Then, (E) -3- (2,4-dihydroxyphenyl) -1- (piperidine) was purified by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1 (volume ratio)). -1-yl) prop-2-en-1-one ((E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one) 0.8 g (15.4 mmol) was obtained.
In a 100 mL flask, 3.00 g (12.1 mmol) of tert-butoxydiphenyl (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one 3.26 ml (14.52 mmol, 1.2 eq) of chlorosilane (Tokyo Chemical Industry Co., Ltd.) was dissolved in 5 mL of dimethyl sulfoxide, and 2.46 g (36.3 mmol, 2.6.3 mmol) of imidazole (Tokyo Chemical Industry Co., Ltd.) was dissolved. 5 eq) was added and stirred overnight. After completion of the reaction, a 5% aqueous sodium hydrogen carbonate solution was added, the mixture was extracted with ethyl acetate, washed with saturated brine, and then dried using magnesium sulfate, whereby the base generator (1) represented by the following formula (7) [1] [ 2.9 g of (E) -3- (4- (tert-butoxydiphenylsilyloxy) -2-hydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one] (5. 63 mmol).

(Production Example 2: Synthesis of base generator (2))
(E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one was obtained in the same manner as in Production Example 1. In a 100 mL flask, 940 mg (3.82 mmol) of (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one, trimethylchlorosilane (Tokyo Chemical Industry) 1.38 g (9.16 mmol, 2.4 eq) dissolved in 5 mL of dimethyl sulfoxide, 1.3 g (19.2 mmol, 5.0 eq) of imidazole (Tokyo Chemical Industry Co., Ltd.) was added, Stir overnight. After completion of the reaction, a 5% aqueous sodium hydrogen carbonate solution was added, the mixture was extracted with ethyl acetate, washed with saturated brine, and then dried using magnesium sulfate to obtain a base generator (2) represented by the following formula (8). 0.51 g was obtained.

(Production Example 3: Synthesis of base generator (3))
(E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one was obtained in the same manner as in Production Example 1. In a 100 mL flask, 940 mg (3.82 mmol) of (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one, tert-butyl vinyl ether (Aldrich) The product was dissolved in a mixed solution of 10 g (manufactured by Co., Ltd.) and 4 g of dehydrated tetrahydrofuran, and 92 mg (0.38 mmol, 0.1 eq) of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight. After completion of the reaction, saturated brine is added, and the mixture is extracted with ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and opened column chromatography (hexane: ethyl acetate = 2: 1 (volume ratio)). By refine | purifying, 260 mg of base generators (3) represented by following formula (9) were obtained.

(Production Example 4: Synthesis of base generator (4))
(E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one was obtained in the same manner as in Production Example 1. In a 100 mL flask, 940 mg (3.82 mmol) of (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one, tert-butyl vinyl ether (Aldrich) Dissolved in a mixed solution of 2.0 ml and 40 ml of dehydrated tetrahydrofuran, and 9.2 mg (0.038 mmol, 0.01 eq) of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Stir. After completion of the reaction, saturated brine is added, and the mixture is extracted with ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and opened column chromatography (hexane: ethyl acetate = 2: 1 (volume ratio)). By refine | purifying, 72 mg of base generators (4) represented by following formula (10) were obtained.

(Production Example 5: Synthesis of base generator (5))
(E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one was obtained in the same manner as in Production Example 1. 3-Chloropropanoic acid trimethylsilyl ester was synthesized with reference to Bulletin des Societes Chimiques Belges, 88 (12), 1043-4; 1979. Subsequently, 1.0 g of (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one in a 100 ml flask under an argon atmosphere (4. 04 mmol), 1.82 g (10.1 mmol) of 3-chloropropanoic acid trimethylsilyl ester was dissolved in 10 ml of methanol and refluxed. 0.24 g (4.44 mmol) of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) was dissolved in 1.0 ml of methanol and slowly added dropwise. After stirring for 3 hours, the mixture was returned to room temperature and filtered. The filtrate was concentrated, dissolved in dichloromethane, washed with water, and purified by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1 (volume ratio)), and expressed by the following chemical formula (11). As a result, 250 mg of the base generator (5) was obtained.

(Production Example 6: Synthesis of base generator (6))
(E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one was obtained in the same manner as in Production Example 1. Subsequently, 1.0 g of (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one in a 100 ml flask under an argon atmosphere (4. 04 mmol), (2-Chloro-ethyl) -carbamic acid tert-butylester (Aurora Fine Chemical) 1.81 g (10.1 mmol) dissolved in 10 ml of methanol And refluxed. 0.24 g (4.44 mmol) of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) was dissolved in 1.0 ml of methanol and slowly added dropwise. After stirring for 3 hours, the mixture was returned to room temperature and filtered. The filtrate was concentrated, dissolved in dichloromethane, washed with water, and purified by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1 (volume ratio)), and expressed by the following chemical formula (12). 250 mg of the base generator (6) was obtained.

(Production Example 7: Synthesis of base generator (7))
In a 30 ml flask, 100 mg (266 μmol) of a base generator (6) and 1 ml of hydrogen chloride (about 4 mol / L 1,4-dioxane solution) (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred for 1 hour. After completion of the reaction, the reaction mixture is concentrated to give (E) -3- (4- (2-aminoethoxy) -2-hydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one (( E) -3- (4- (2-aminoethoxy) -2-hydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one) was obtained quantitatively. Subsequently, all of (E) -3- (4- (2-aminoethoxy) -2-hydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one obtained above Was dissolved in 10 ml of toluene, and a mixed solution of 14.3 mg (0.32 eq) of triphosgene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.5 ml of toluene was added dropwise in a state cooled to 0 ° C. After stirring for 10 minutes at the same temperature, the temperature was raised to 95 ° C. over 2 hours. Furthermore, after heating up to 112 degreeC over 2 hours, it cooled and prepared the isocyanate solution. Subsequently, 41 mg (1.2 eq) of ethyl acetoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 μl of sodium methoxide (about 5 mol / L methanol solution) (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and 1 at 80 ° C. Stir for hours. After completion of the reaction, the reaction product is concentrated and purified by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1 (volume ratio)) to produce a base generator (7) represented by the following chemical formula (13). 20 mg of was obtained.

(Production Example: Synthesis of Base Generator (8))
1,1-dimethylethyl N- (2-chloroethyl) -N-methylcarbamate was synthesized according to a report (J. Med. Chem. 1998, 41, 5429-5444).
In the same manner as in Production Example 1, (E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one ((E) -3- ( 2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one) was obtained.
(E) -3- (2,4-dihydroxyphenyl) -1- (piperidin-1-yl) prop-2-en-1-one 1.0 g (4.04 mmol) in a 100 ml flask under argon atmosphere Then, 1.96 g (10.1 mmol) of 1,1-dimethylethyl N- (2-chloroethyl) -N-methylcarbamate was dissolved in 10 ml of methanol and refluxed. 0.24 g (4.44 mmol) of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) was dissolved in 1.0 ml of methanol and slowly added dropwise. After stirring for 3 hours, the mixture was returned to room temperature and filtered. The filtrate was concentrated, dissolved in dichloromethane, washed with water, and purified by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1 (volume ratio)), and expressed by the following chemical formula (14). 120 mg of the base generator (8) was obtained.

(Production Example 9: Synthesis of base generator (9))
In a 300 mL flask, 8.5 g (50 mmol) of 5-hydroxy-2-nitrobenzyl alcohol (Aldrich), di-tert-butyl dicarbonate (Tokyo Chemical Industry Co., Ltd.) 13.1 g (60 mmol, 1.2 eq) ), 10.5 ml (75 mmol, 1.5 eq) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 mL of chloroform and stirred overnight. After completion of the reaction, saturated brine was added and the mixture was extracted with ethyl acetate, washed with saturated brine, and dried over magnesium sulfate to obtain 160 mg of tert-butyl-3- (hydroxymethyl) -4-nitrophenyl carbonate. It was.
Under a nitrogen atmosphere, 6.7 g (25 mmol) of tert-butyl-3- (hydroxymethyl) -4-nitrophenyl carbonate was dissolved in 100 ml of dehydrated dimethylacetamide in a 200 ml three-necked flask, and 7.0 ml (50 mmol, 2.0 eq) of triethylamine was dissolved. Was added. In an ice bath, 5.5 g (27 mmol, 1.1 eq) of 4-nitrophenyl chloroformate (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into 2 L of water, and the resulting precipitate was filtered and purified by silica gel column chromatography to obtain 6.4 g of carbamate precursor A.
In a 100 ml three-necked flask in a nitrogen atmosphere, 4.1 g (9.5 mmol) of the carbamate precursor A was dissolved in 50 ml of dehydrated dimethylacetamide, and 3.2 ml (37 mmol, 3.9 eq) of piperidine, 1-hydroxybenzotriazole (Tokyo Kasei ( 0.36 g (0.3 eq) was added, and the mixture was stirred with heating at 90 ° C. for 18 hours. The reaction solution was poured into 1 L of 1% aqueous sodium hydrogen carbonate solution, and the resulting precipitate was filtered and washed with water to obtain 1.2 g of a base generator (9) represented by the following chemical formula (15). .

(Production Example 10: Synthesis of base generator (10))
According to a previous report (European Journal of Medicinal Chemistry (2009), 44 (1), 109-116), (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone oxime ((E)- (2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone oxime) was synthesized.
In a 100 ml eggplant flask, 2.79 g (10 mmol) of (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone oxime, 1.47 g of cyclohexanecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 mmol, 1.0 eq) was dissolved in 30 mL of chloroform. After cooling with ice water, 1.67 ml (12 mmol, 1.2 eq) of triethylamine diluted with 5 mL of chloroform was added dropwise. After stirring at room temperature for 1 hour, the reaction solution was washed with water three times. The organic layer was dehydrated with magnesium sulfate, filtered, and concentrated to give (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone o-cyclohexanecarbonyloxime ((E)-(2- 0.7 g of hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone O-cyclohexanecarbonyl oxime) was obtained.
In a 100 ml flask, (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone o-cyclohexanecarbonyloxime 0.6 g (1.60 mmol) di-tert-butyl dicarbonate (Tokyo Chemical Industry ( 420 mg (1.92 mmol, 1.2 eq) and 330 μl (2.40 mmol, 1.5 eq) of triethylamine (Tokyo Chemical Industry Co., Ltd.) were dissolved in 10 mL of chloroform and stirred overnight. After completion of the reaction, saturated brine was added, extracted with ethyl acetate, washed with saturated brine, and dried using magnesium sulfate to obtain 120 mg of a base generator (10) represented by the following chemical formula (16). .

(Production Example 11: Synthesis of base generator (11))
(E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone oxime was synthesized according to a report (European Journal of Medicinal Chemistry (2009), 44 (1), 109-116).
In a 200 mL three-necked flask under nitrogen atmosphere, 2.79 g (10 mmol) of (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone oxime was dissolved in 50 mL of dehydrated dimethylacetamide, An amount of dibutyltin diacetate (manufactured by Kanto Chemical Co., Inc.) was added and stirred. Thereto was added 1.25 g (10 mmol) of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was heated and stirred at 105 ° C. for 7 hours. Thereafter, reprecipitation was performed with 500 ml of distilled water, and the precipitate was collected and purified by column chromatography. (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone o-cyclohexylcarbamoyl 2.1 g of oxime ((E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone O-cyclohexylcarbamoyl oxime) was obtained.
In a 100 ml flask, 1.5 g (3.71 mmol) of (E)-(2-hydroxynaphthalen-1-yl) (4-hydroxyphenyl) methanone o-cyclohexylcarbamoyloxime di-tert-butyl dicarbonate (Tokyo Chemical Industry ( 971 mg (4.45 mmol, 1.2 eq) and triethylamine (Tokyo Chemical Industry Co., Ltd.) 780 μl (5.60 mmol, 1.5 eq) were dissolved in 30 mL of chloroform and stirred overnight. After completion of the reaction, saturated brine was added and the mixture was extracted with ethyl acetate, washed with saturated brine, and dried using magnesium sulfate to obtain 340 mg of a base generator (11) represented by the following chemical formula (17). .

(Comparative Production Example 1: Synthesis of Comparative Base Generator (1))
Moreover, the compound represented by following Chemical formula (18) was synthesize | combined according to description of Unexamined-Japanese-Patent No. 2009-80452 as a comparison base generator (1).

[Evaluation of base generator]
The synthesized base generators (1) to (11) and the comparative base generator (1) were measured and evaluated as follows. The results of the molar extinction coefficient are shown in Table 1. Table 2 shows the results of the base generating ability. In Table 2, the base generation rate is a percentage of the number of moles of the generated base relative to the number of moles of the base generator used. The base generators (1) to (11) and the comparative base generator (1 ) Base generation rate is a ratio of light irradiation and heating combined.

(1) Molar extinction coefficient The base generators (1) to (11) and the comparative base generator (1) were each dissolved in acetonitrile at a concentration of 1 × 10 ⁻⁴ mol / L, and a quartz cell (optical path length 10 mm) was obtained. ) Was filled with the solution, and the absorbance 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) Base generating ability Base generating ability was evaluated using NMR measurement. The base generation rate is a percentage of the number of moles of the generated base with respect to the number of moles of the base generator used, and the base generation of the base generators (1) to (11) and the comparative base generator (1). The rate is the ratio of light irradiation and heating combined.
For the base generators (1) to (11) and the comparative base generator (1), three 1 mg samples were prepared, and each was dissolved in 0.5 mL of heavy dimethyl sulfoxide in a quartz NMR tube.
About the base generators (1) to (11) and the comparative base generator (1), using a filter that transmits 20% of i-line and a high-pressure mercury lamp, one is irradiated with light at ² J / cm ² , etc. One of these was irradiated with light at 20 J / cm ² . The remaining one was not irradiated with light. In addition, ¹ H NMR was measured to determine the ratio of isomerization or base generation.
When the base generators (1) and (4) to (8) were heated at 160 ° C. for 10 minutes using an oil bath, about 95% of the isomerized compounds generated amines. Since the base generators (2) and (3) have a protecting group in the phenolic OH site, the cyclization reaction proceeds at the same time as the deprotection reaction is started by heating at 160 ° C. for 10 minutes. About 90% of the compounds generated amine by heating for 50 minutes. In addition, the base generators (1) to (5) and (8) to (11) are heated at 160 ° C. for 10 minutes to initiate a reaction in which a part of the substituents are changed. ) And (7) were heated at 120 ° C. for 10 minutes to initiate a reaction in which part of the substituents were changed. Base generators (9) to (11) generated amines only by light irradiation. Base generators (1) to (8) generated amines with high sensitivity by light irradiation and heating.
Table 2 shows the evaluation results of the base generating ability.

(Examples 1 to 9: Preparation of photosensitive resin compositions (1) to (9))
Using the base generators (1) to (5) and (8) to (11) obtained in Production Examples 1 to 5, photosensitive resin compositions (1) to (9) having the compositions shown below were prepared. did.
Epoxy resin (YP50EK35 (phenoxy resin), 35% by weight methyl ethyl ketone solution manufactured by Nippon Steel Chemical Co., Ltd.): 100 parts by weight Base generator: 35 parts by weight

The photosensitive resin compositions (1) to (9) were 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 one of the coating films of the photosensitive resin compositions (1) to (6), 10 J / cm ² entire surface exposure was performed with a high-pressure mercury lamp using a manual exposure machine. About one of the coating films of the photosensitive resin compositions (7) to (9), 100 J / cm ² entire surface exposure was performed with a high-pressure mercury lamp using a manual exposure machine. Thereafter, each coating film was heated at 150 ° C. for 60 minutes. The cured film was dissolved in deuterated dimethyl sulfoxide, and NMR measurement of the deuterated dimethyl sulfoxide solution was conducted. As a result, no coumarin derivative formed simultaneously with the generation of amine was detected. It became clear that it was immobilized.
According to the above embodiment, the base generator having a blocked covalent bond forming group that is partially changed in structure by heating and / or irradiation with an electromagnetic wave to become a hydroxyl group or an amino group is fixed to a polymer precursor having an epoxy group. It was revealed that Moreover, even if it is any of the base generator represented by the said Chemical formula (1-1), the said Chemical formula (1-2), or the said Chemical formula (1-3), it is the polymer precursor which has an epoxy group similarly. The immobilization on the body was confirmed.

(Comparative Example 1: Preparation of comparative photosensitive resin composition (1))
A comparative photosensitive resin composition (1) having the composition shown below was prepared using the comparative base generator (1).
Epoxy resin (YP50EK35 (phenoxy resin), 35% by weight methyl ethyl ketone solution manufactured by Nippon Steel Chemical Co., Ltd.): 100 parts by weightComparative base generator (1): 1 part by weight Comparative base generator (1) is an acetone-based solvent, Since it is difficult to dissolve in methyl ethyl ketone, a resin composition containing a base generator at the same concentration as in the present invention could not be prepared. A coating film was prepared with a comparative photosensitive resin composition (1) in which a comparative base generator was slightly dissolved (about 3.0% by weight), and exposure and post-exposure baking were performed. However, the coating film was not cured. It was revealed. Further, the coating film that had been baked after exposure was dissolved in heavy dimethyl sulfoxide, and NMR measurement of the heavy dimethyl sulfoxide solution was carried out. As a result, a coumarin derivative formed simultaneously with the generation of amine was detected.

(Examples 10 to 20: Preparation of photosensitive resin compositions (10) to (20))
Hexamethylene diisocyanate (manufactured by Kanto Chemical Co.) as an isocyanato resin 100 parts by weight, polyhydroxytetrahydrofuran (manufactured by Aldrich) as a resin having a hydroxyl group 150 parts by weight, base generators (1) to (11) 10 parts by weight, tetrahydrofuran 500 parts by weight The photosensitive resin composition (10)-(20) which consists of was prepared.
Each of the photosensitive resin compositions (10) to (20) was spin-coated on a chromium-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 of the photosensitive resin composition 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 30 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.
The cured film was dissolved in deuterated dimethyl sulfoxide, and NMR measurement of the deuterated dimethyl sulfoxide solution was conducted. As a result, no coumarin derivative formed simultaneously with the generation of amine was detected. It became clear that it was immobilized.
According to the above-described embodiment, the base generator having a blocked covalent bond forming group as a substituent, which is partly changed in structure by heating and / or irradiation with electromagnetic waves and becomes an isocyanato group, a hydroxyl group or an amino group, has an isocyanato group. It was revealed that it was immobilized on a polymer precursor.

Claims (11)

  Blocking covalent bond formation that is a base generator that generates a base upon irradiation with electromagnetic waves, and becomes a functional group capable of forming a covalent bond with other molecules by changing part of the structure upon heating and / or irradiation with electromagnetic waves A base generator having one or more groups in one molecule.   The base generator according to claim 1, wherein the functional group capable of forming a covalent bond with the other molecule is an isocyanato group, a thioisocyanato group, a hydroxyl group, a carboxyl group, or an amino group. The base generator according to claim 1 or 2, represented by the following chemical formula (1-1), the following chemical formula (1-2), or the following chemical formula (1-3).

(In Formula (1-1), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. R ¹ and R ² are bonded to each other. May 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. Atom, halogen atom, 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 There may be different even in the same ^{.R 5, R 6,} R ⁷ and ^{R 8} each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, shea Nord 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, which may be the same or different R ⁵ , R ⁶ , R ^7, and R ⁸ may be bonded to each other to form a cyclic structure, and may include a hetero atom bond, provided that R ³ , A block in which at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a functional group capable of forming a covalent bond with another molecule by changing a part of the structure by heating and / or irradiation with electromagnetic waves. R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

(In Formula (1-2), R ¹ and R ² are each independently a hydrogen atom or an organic group, and may be the same or different. R ¹ and R ² are bonded to each other. may form a cyclic structure Te, may contain a binding heteroatom. proviso that at least one of R ¹ and R ² is an organic group .R ¹⁰ and R ^{10 'are} each independently hydrogen An atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, and R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ are each independently a hydrogen atom or a halogen atom; , 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, amino group An ammonio group or an organic group, may be different even in the same ^{.R 11, R 12, R 13} , R 14 and ^{R 15,} to form a cyclic structure two or more of them are combined However, at least one of R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ may be partially changed by heating and / or irradiation with electromagnetic waves. And has a blocked covalent bond forming group that becomes a functional group capable of forming a covalent bond with another molecule.)

(In Formula (1-3), R ¹⁷ is an amino group or an organic group substituted with an organic group, and R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a halogen atom, a sulfide group, a silyl group, or a 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, which may be the same or different , R ¹⁸ and R ¹⁹ are each an aromatic compound optionally having a hetero atom, and two or more of R ¹⁷ , R ¹⁸ and R ¹⁹ are combined to form a cyclic structure. even if well, at least one good .R ¹⁸ and R ¹⁹ may contain a binding heteroatom, heating and / or electromagnetic waves other molecules co portion of the structure is changed by irradiation of Having a functional group capable of forming a bond blocking covalent bonding group.) The blocked covalent bond-forming groups are the following (i) to (iv):
(I) a structure in which the hydrogen atom at the terminal of the hydroxyl group is substituted with one or more selected from the group consisting of organic groups represented by the following formulas (2-1) to (2-6);
(Ii) One or more selected from the group consisting of an organic group represented by the following formula (2-1), an organic group represented by the following formula (2-3), and an organic group in which the terminal hydrogen atom of the carboxyl group Structure replaced with
(Iii) a structure in which one hydrogen atom at the terminal of the amino group is substituted with an organic group represented by the following formula (2-2), and
(Iv) one or more structures selected from the group consisting of substituents represented by the following formula (3-1) to the following formula (3-6);
The base generator according to any one of claims 1 to 3, comprising at least one structure selected from the group consisting of:

(In the formula (2-1), R ³⁰ , R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom or an organic group, R ³³ is an organic group, and R ³⁰ , R ³¹ , R ³² , R ³³ may be bonded to each other to represent a cyclic structure, and in formula (2-2), R ³⁴ is an organic group, and in formula (2-3), R ³⁵ , R ³⁶ , R ³⁷ 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 is an organic group.)

(In Formula (3-1), Q is an oxygen atom or a sulfur atom, R ⁴² is an organic group. In Formula (3-2), Ew is each independently an electron-withdrawing group, and Q is oxygen. In formula (3-3), Q is an oxygen atom or sulfur atom, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an organic group, in formula (3-4), Q is an oxygen atom or a sulfur atom, and n is 3-7.)   A photosensitive resin composition comprising a polymer precursor whose reaction to a final product is promoted by heating with a basic substance or in the presence of a basic substance, according to any one of claims 1 to 4. A photosensitive resin composition comprising the described base generator as an essential component.   6. The polymer precursor according to claim 5, wherein the polymer precursor has a functional group capable of forming a covalent bond with a functional group capable of forming a covalent bond with the other molecule of the base generator. Photosensitive resin composition.   The polymer precursor is selected from the group consisting of a compound and polymer having an epoxy group, an isocyanato group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzoxazole precursor. The photosensitive resin composition of Claim 5 or 6 characterized by including the above.   Any one of Claims 5 to 7 used as a forming material for 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.   A pattern forming material comprising the photosensitive resin composition according to claim 5.   A coating film or a molded body is formed using the photosensitive resin composition according to any one of claims 5 to 8, and the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern, and after irradiation or irradiation A method for producing a relief pattern, wherein heating is performed at the same time to change the solubility of the irradiated portion, followed by development.   Printed matter, paint, sealant, adhesive, display device, semiconductor device, electronic component, microscopic part, at least part of which is formed by the photosensitive resin composition according to any one of claims 5 to 8 or a cured product thereof. An article that is an electromechanical system, an optically shaped object, an optical member, or a building material.