JP5910245B2 - Base generator, photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, relief pattern manufacturing method using the photosensitive resin composition, and article - Google Patents

Description

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

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

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

  Various methods have been proposed as means for forming a pattern using a polyimide precursor. As a patterning method, by mixing a photobase generator with the polyamic acid of the polyimide precursor and heating after exposure, the cyclization proceeds by the action of the base generated by exposure, and the solubility in the developer is reduced. A method for obtaining a polyimide pattern by forming a pattern by increasing the contrast of the dissolution rate of the exposed portion and the unexposed portion with respect to the developer and then imidizing is reported (Patent Document 1).

  As another example of the photosensitive resin composition using the photobase generator, there is an example using an epoxy compound (for example, Patent Document 2). 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.

  However, a normal photobase generator generates a base upon irradiation with light, so that depending on the resin to be combined, curing proceeds immediately after irradiation with light, and there is a possibility that the pot life is short and the workability is poor.

  On the other hand, Non-Patent Document 1 describes that a compound obtained by an addition reaction between phthalide or 3-isochromanone and pyrrolidine generates an amine by heating and initiates polymerization of epoxide. Since the compound generates an amine only by heating, it cannot be used for pattern formation like the photobase generator, and there are problems in heat resistance and storage stability.

  In Non-Patent Document 2, two hydroxy groups of 4,4 ′-(1,3-propanediyl) N, N′-bis [(2-hydroxymethyl) benzoylpiperidine] are each protected with a tetrahydropyranyl group. Compounds are described. According to Non-Patent Document 2, it is described that when the compound is used in combination with a photoacid generator, a tetrahydropyranyl group is deprotected with an acid generated by light irradiation and further heated to generate an amine. ing. From such an action, in order to use the compound like a photobase generator, there is a problem that a photoacid generator is essential. In addition, since the tetrahydropyranyl group is easily deprotected by an acid, the compound functions like a photobase generator in an acidic environment, for example, when combined with an acidic compound such as polyamic acid. There was a fear of not.

JP-A-8-227154 Japanese Patent Laid-Open No. 2003-212856

Polymer Preprints, Japan Vol.59, No.1 (2010), p.563 Journal of photopolymer science and technology, 20, 2, 299-302

  The present invention has been made in view of the above circumstances, and its main object is a base generator having excellent heat resistance and storage stability, capable of adjusting the pot life, and having a wide range of applicable compounds to be combined, and Another object of the present invention is to provide a photosensitive resin composition that is excellent in heat resistance and storage stability, can be adjusted in pot life, and can form a pattern having a good shape.

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

(In the chemical formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group that may contain a substituent, and may be the same or different, and R ¹ and R ² May combine to form a cyclic structure, provided that at least one of R ¹ and R ² is a hydrocarbon group which may contain a substituent, and R ³ and R ⁴ are each independently hydrogen Represents an atom or a substituent, and may be the same or different, and when there are a plurality of R ³ and R ⁴ , a plurality of R ³ and a plurality of R ⁴ may be the same or different from each other; which may be .R ^{5, R 6, R 7} and R ⁸ each independently represent a hydrogen atom or a substituent, those two or more are combined to optionally form a cyclic structure .R ⁹ And R ¹⁰ is a hydrogen atom , and R ¹¹ is removed only by electromagnetic wave irradiation. (Protective group which can be protected. M and n each represent the number of repeating units, m is 1 and n is 0. )

  The photosensitive resin composition according to the present invention comprises a polymer precursor whose reaction to the final product is promoted by a basic substance or by heating in the presence of the basic substance, and the base according to the present invention. It contains a generator.

In base generator according to the present invention, in Formula (1), since m + n is 1, excellent heat resistance and storage stability, efficiency of generating base is preferable from the viewpoint of improving.

In the base generator according to the present invention, in the chemical formula (1), R ¹¹ is a protecting group represented by the following chemical formula (2-1) or the following chemical formula (2-2). In addition, it is preferable from the viewpoint of excellent storage stability and easy elimination reaction due to irradiation of electromagnetic waves.

(In the chemical formula (2-1), R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and may be the same or different. K is 1 or 2. k is 1. In the case of 2, a plurality of R ¹² and a plurality of R ¹³ may be the same or different from each other, and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a substituent. Represents a group, and two or more of them may combine to form a cyclic structure.
In chemical formula (2-2), R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a substituent, and may be the same or different. R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and two or more of R ²⁰ , R ²¹ , R ²² and R ²³ are bonded to form a cyclic structure May be formed. )

  In the photosensitive resin composition according to the present invention, the polymer precursor is a compound and polymer having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzo. The inclusion of one or more selected from the group consisting of oxazole precursors is preferred from the standpoint of obtaining a pattern with excellent sensitivity and good shape.

  The photosensitive resin composition according to the present invention is a paint, a printing ink, a sealing material, or an adhesive, or a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped object, an optical member, or a building material. It can use suitably for material.

  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 photosensitive resin composition which concerns on the said invention.
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 according to the present invention, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, It develops, after heating or simultaneously with irradiation, and changing the solubility of the said irradiation site | part, and developing.

  According to the method for producing a relief pattern according to the present invention, by using a combination of the polymer precursor and the base generator according to the present invention, a coating film or a molded body made of a photosensitive resin composition is used. A pattern for performing development can be formed without using a resist film for protecting the surface from the developer.

  The present invention also provides a printed material, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectricity, which is at least partially formed from the photosensitive resin composition according to the present invention or a cured product thereof. Articles of any of mechanical systems, stereolithography, optical members or building materials are also provided.

  According to the present invention, the base generator is excellent in heat resistance and storage stability, the pot life can be adjusted, the range of application of the compound to be combined is wide, and the heat resistance and storage stability are excellent. A photosensitive resin composition that can be adjusted and can form a pattern having a good shape can be provided.

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.
In the present invention, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam, unless the wavelength is specified. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure. Note that electromagnetic waves with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.

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

(In the chemical formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group that may contain a substituent, and may be the same or different, and R ¹ and R ² there bound good .R ³ and R ⁴ may form a cyclic structure each independently represent a hydrogen atom or a substituent, good .R ³ and R ⁴ be different even in the same A plurality of R ^{3 s} and a plurality of R ^{4 s} may be the same or different from each other, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, or Represents a substituent, and two or more of them may combine to form a cyclic structure, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and may be the same or different. If which may be .R ⁹ and ^{R 10} are a plurality, a plurality of ^{R 9} Judges, and plural R ¹⁰ together are optionally being the same or different .R ¹¹ is only the irradiation of the electromagnetic wave is a protective group which can be deprotected .m and n represents the number of repeating units, respectively, m is an integer of 0 or more, n is an integer of 0 or more, provided that m + n is an integer of 1 or more.)

The base generator of the present invention has a structure of the above chemical formula (1) in which a hydroxy group is protected by a protective group that can be deprotected only by irradiation with electromagnetic waves. Since the base generator of the present invention has such a specific structure, as shown in the following scheme 1, the hydroxy group is first deprotected by irradiation with an electromagnetic wave and then deprotected by further heating. A cyclization reaction involving the reaction proceeds to produce a base (NHR ¹ R ² ).

Since the base generator of the present invention does not generate a base unless it is further subjected to a procedure of heating after irradiation of an electromagnetic wave in this way, it generates a base only by heating like a conventional thermal base generator. It has better heat resistance and storage stability than a base generator and is easy to handle. Further, the base generator of the present invention can be patterned by exposure in the same manner as conventional photobase generators. On the other hand, unlike the conventional photobase generator, the base generator of the present invention does not generate a base only by irradiation with electromagnetic waves. For example, a resin that cures immediately in the presence of a base. It is easy to handle even when combined with it, and since it is possible to generate amine by heating after irradiation of electromagnetic waves, it is excellent in workability and can be applied to a wide range of resins. .
Furthermore, since the base generator of the present invention uses a protective group that can be deprotected only by irradiation with electromagnetic waves, there is no need to combine it with a photoacid generator or the like, and it can be used alone as a photobase generator and handled. Easy. Unlike the non-patent document 2, the base generator of the present invention can be used without problems even in an acidic environment such as when combined with an acidic compound such as polyamic acid, because a protective group that can be deprotected only by irradiation with electromagnetic waves is used. In addition, when used as a photosensitive resin composition, unlike an acid, a base does not cause metal corrosion, so that a more reliable cured film can be obtained and the heat resistance and stability of the final product are improved.
In addition, existing photobase generators and photoacid generators generate bases or acids upon light irradiation, making it impossible to adjust the pot life, for example, for applications such as bonding substrates that do not transmit light. It was difficult to use. Since the base generator of the present invention does not generate a base only by light irradiation, it is possible to adjust the pot life, and for example, it is possible to perform operations such as bonding substrates after light irradiation.

In the chemical formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group that may contain a substituent, and may be the same or different, and R ¹ and R ² may be the same. It may be bonded to have a cyclic structure.
The hydrocarbon group in R ¹ and R ² may include a branched chain in addition to a straight chain, and two or more branched chains included in the hydrocarbon group are combined to form a cyclic structure. May be. Here, the branched chain refers to a structure having a branched hydrocarbon group, and also refers to each branched hydrocarbon group included in the structure.
The hydrocarbon group may contain an unsaturated bond, and examples thereof include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, and an aralkyl group. These hydrocarbon groups may contain a substituent in the hydrocarbon group.
The cyclic structure to which the branched chain is bonded is at least two selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, condensed rings, and heterocyclic rings, and the alicyclic hydrocarbons, condensed rings, and heterocyclic rings. It may be a structure in which are combined.
The hydrocarbon group in R ¹ and R ² is usually a monovalent hydrocarbon group, but the generated NHR ¹ R ² is a basic substance having two or more NH groups capable of forming an amide bond such as diamine. In some cases, it can be a divalent or higher valent hydrocarbon group.

  Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of these hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and propyl groups, alkenyl groups having 1 to 20 carbon atoms such as vinyl and allyl groups, ethynyl groups, An alkynyl group having 1 to 20 carbon atoms such as a 2-propynyl group, a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, a xylyl group and a fluorenyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, a phenethyl group, It has 4 to 23 carbon atoms such as aralkyl group having 7 to 20 carbon atoms such as 3-phenylpropyl group, cycloalkyl group having 4 to 23 carbon atoms such as cyclopentyl group and cyclohexyl group, cyclopentenyl group and cyclohexenyl group. A cycloalkenyl group etc. are mentioned.

In the present invention, the substituent means an atom or atomic group other than a hydrogen atom that can be replaced with a hydrogen atom. As the substituent, for example, an atomic group which can be represented by -XR ^25. Here, X is a direct bond or a divalent linking group, and -XR ²⁵ is X and R ²⁵ which is an atom or atomic group other than hydrogen that can be replaced with a hydrogen atom or a hydrogen atom. There is no particular limitation as long as it is an atomic group in which is connected. However, the case where X is a direct bond, R ²⁵ is a hydrogen atom, and -XR ²⁵ is a hydrogen atom is excluded.

X in the substituent —XR ²⁵ is not particularly limited as long as it is a direct bond or a divalent linking group. For example, a bond composed of an oxygen atom or a sulfur atom, a carbon atom, a silicon atom , An oxygen atom, a sulfur atom, a nitrogen atom, and / or an atomic group containing a phosphorus atom. Examples of X in the case of a divalent linking group include an oxy group (—O—), a thio group (—S—), a carbonyl group (—C (═O) —), and an oxycarbonyl group (—C (= O) -O-), thiocarbonyl group (-C (= S)-), oxythiocarbonyl group (-C (= S) -O-), carbonyloxy group (-O-C (= O)-) Oxycarbonyloxy group (—O—C (═O) —O—), carbonylthio group (—S—C (═O) —), oxycarbonylthio group (—S—C (═O) —O—) ), A sulfinyl group (—S (═O) —), a sulfonyl group (—S (═O) ₂ —) and the like.
X in the substituent —XR ²⁵ is an oxy group, a thio group, a carbonyl group, an oxycarbonyl group, a thiocarbonyl group, an oxythiocarbonyl group, or a carbonyl group from the viewpoint of improving compatibility with a resin or solubility in a solvent. An oxy group, an oxycarbonyloxy group, and a carbonylthio group are preferable, and an oxy group and a thio group are more preferable.

In the substituent —XR ²⁵ , R ²⁵ is a hydrogen atom or an atom or atomic group other than hydrogen that can be replaced with a hydrogen atom. R ²⁵ is, for example, a halogen atom (—F, —Cl, —Br, —I), a hydroxyl group, a mercapto group, a cyano group, an isocyano group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, a sulfo group, Examples thereof include a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group that may contain a substituent, a hydrocarbon group that may contain a substituent, a silyl group that may contain a substituent, and an amino group that may contain a substituent.
Here, in the base generator of this invention, it is preferable not to contain the basic amino group as a substituent. If an amino group having basicity is contained, the base generator itself becomes a basic substance, which accelerates the reaction and may reduce the difference in solubility contrast between the exposed and unexposed areas. Because there is. However, when there is a difference in basicity between the irradiation with electromagnetic waves and the base generated after heating, such as when an amino group is bonded to the aromatic ring present in the substituent of R ¹ or R ^2. May be used even if an amino group is contained in the substituent of R ¹ or R ² , and the amino group is not excluded as a substituent.

As the hydrocarbon group which may contain a substituent in R ²⁵ , the hydrocarbon group may contain an unsaturated bond, may contain a branched chain, and two or more branched chains may be bonded. A cyclic structure may be formed, and two or more branched chains containing a substituent may be bonded to form a heterocyclic ring. The heterocycle may be an aliphatic heterocycle having no aromaticity or an aromatic heterocycle having aromaticity, and examples thereof include cyclic ethers, lactones, lactams, and aromatic heterocycles. . Examples of the hydrocarbon group that may contain a substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a heterocyclic group. Examples of these hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and propyl groups, alkenyl groups having 1 to 20 carbon atoms such as vinyl and allyl groups, ethynyl groups, An alkynyl group having 1 to 20 carbon atoms such as a 2-propynyl group, a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, a xylyl group and a fluorenyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, a phenethyl group, It has 4 to 23 carbon atoms such as aralkyl group having 7 to 20 carbon atoms such as 3-phenylpropyl group, cycloalkyl group having 4 to 23 carbon atoms such as cyclopentyl group and cyclohexyl group, cyclopentenyl group and cyclohexenyl group. Cycloalkenyl group, ethylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, β-propiolactone γ-butyrolactone, σ-valerolactone, ε-caprolactone, β-propiolactam, γ-butyrolactam, σ-valerolactam, ε-caprolactam, furan ring, thiophene ring, 2H-pyran ring, 4H-thiopyran ring, benzofuran ring , 1-benzothiophene ring, 2H-chromene ring, 1H-2-benzopyran ring, xanthene ring, heterocyclic ring group in which one hydrogen is removed from a heterocyclic ring, methoxymethyl group, ethoxymethyl group, propoxymethyl group And an aryloxyalkyl group having 7 to 26 carbon atoms such as an alkyloxyalkyl group having 2 to 20 carbon atoms, such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group. In addition, the substituent which may be included may be the same as the substituent —XR ²⁵ .

Examples of the silyl group that may contain a substituent in R ²⁵ include an alkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group, a trimethoxysilyl group, a dimethoxymethyl group, and a methoxydimethyl group. An alkoxysilyl group etc. are mentioned. The substituent which may be included may be the same as the substituent —XR ²⁵ .

Examples of an amino group (—NH (—R ²⁶ ), —N (—R ²⁷ ) (— R ²⁸ )) that may contain a substituent in R ²⁵ include R ²⁶ , R ²⁷ , and R ^28. And a hydrocarbon group that may contain a heteroatom bond at the bond terminal with the nitrogen atom and may contain a substituent. The hydrocarbon group that may contain a heteroatom bond at the bond terminal to the nitrogen atom and may contain a substituent may be the same as the substituent -XR ²⁵ as long as it can be bonded to the nitrogen atom.
Preferred examples of the amino group that may contain a substituent include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, and N-alkyl-N-arylamino. Group, acylamino group, N-alkylacylamino group, N-arylacylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonyl Examples include an amino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group.

Examples of -XR ²⁵ include halogen atoms (-F, -Cl, -Br, -I), hydroxyl groups, mercapto groups, cyano groups, isocyano groups, nitro groups, nitroso groups, carboxyl groups, carboxylate groups, sulfo groups. A group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a hydrocarbon group that may contain the above substituents (hereinafter sometimes referred to as “the above-mentioned hydrocarbon group”), a silyl group that may contain the above substituents, An alkoxy group having 1 to 20 carbon atoms such as amino group, methoxy group, ethoxy group, isopropyloxy group, t-butoxyoxy, ethylhexyloxy group, cyclohexyloxy group (-OR ²⁹ , where R ²⁹ is above a hydrocarbon group), a benzyloxy group, an aryloxy group such as naphthyloxy group (-OAr, where Ar has a substituent Also aryl group), an acetoxy group, an acyloxy group (-OCOR ³⁰ such benzoyloxy group, wherein ^{R 30} is a hydrocarbon group as described above), a carbamoyloxy group ^{(-OCONR 31 R 32: R 31} , R 32 Each independently represents a hydrogen atom or the above-described hydrocarbon group, which may be the same or different, and R ³¹ and R ³² may be bonded to each other), a cyanooxy group (cyanato group) (—OCN) Alkylthio groups having 1 to 20 carbon atoms such as methylthio group and ethylthio group (-SR ³³ : R ³³ is the above-mentioned hydrocarbon group), arylthio groups such as phenylthio group and naphthylthio group (-SAr: Ar has a substituent) aryl group which may be,), acetylthio group, an acylthio group such as benzoylthio group ^{(-SCOR 34: R} 34 is above a hydrocarbon group), shea Thio (thiocyanato group) (- SCN), a formyl group (-COH), acyl group ^{(-COR 35: R 35} is above a hydrocarbon group), an alkoxycarbonyl group ^{(-COOR 36: R 36} is above the hydrocarbon Group), an aryloxycarbonyl group such as a benzyloxycarbonyl group (—COOAr: Ar is an aryl group which may have a substituent), a carbamoyl group (—CONR ³⁷ R ³⁸ : R ³⁷ , R ³⁸ are each independently hydrogen. An atom or the above-described hydrocarbon group, which may be the same or different, and R ³⁷ and R ³⁸ may be bonded to each other; a thioacyl group (—CSR ³⁹ : R ³⁹ is the above-mentioned hydrocarbon group; ), An alkoxythiocarbonyl group (—CSOR ⁴⁰ : R ⁴⁰ is the hydrocarbon group described above).

In the chemical formula (1), the cyclic structure formed by combining R ¹ and R ² includes a saturated or unsaturated alicyclic hydrocarbon, a condensed ring, a heterocyclic ring, and the alicyclic hydrocarbon. The structure may be a combination of two or more selected from the group consisting of a condensed ring and a heterocyclic ring.

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. When the generated NHR ¹ R ² is a basic substance having two or more NH groups, an NH group capable of forming an amide bond is formed at one or more terminals of R ¹ and / or R ^{2 in} the chemical formula (1). The structure which the photolatent part which generate | occur | produces the base which has by irradiation of electromagnetic waves and a heating has couple | bonded further is mentioned. As the photolatent site, to one or more ends of the R ¹ and / or R ² of Formula (1), residues obtained by removing R ¹ and / or R ² is further bonded of formula (1) Structure.

  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, di-2-propanolamine, bis (2-methoxyethyl) amine, ethylmethylamine, N-methylpropylamine, N -Methylbutylamine, N-methylisobutylamine, N-tert-butylmethylamine, N-methylcyclohexylamine, N-isopropylcyclohexylamine, N-ethylcyclohexylamine, N-methyladamantan-1-amine, 3-methylamino- 1,2-propanediol, methylaminoacetaldehyde dimethyl acetal, N-methyl-3-ethoxypropylamine, N-methyl-3-propoxypropylamine, N-methyl-3-butoxypropylamine, N-methyl Ru-3-isopropoxypropylamine, N-methyl-3-heptyloxypropylamine, N-methyl-3- (2-ethylhexyloxy) propylamine, N-methyltetrahydrofurfurylamine, aziridine, azetidine, pyrrolidine, piperidine , Azepan, Azocan, Methylaziridine, Dimethylaziridine, Methylazetidine, Dimethylazetidine, Trimethylazetidine, Methylpyrrolidine, Dimethylpyrrolidine, Trimethylpyrrolidine, Tetramethylpyrrolidine, Methylpiperidine, Dimethylpiperidine, Trimethylpiperidine, Tetramethylpiperidine, Penta Methylpiperidine, 4-hydroxypiperidine, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 4-piperidineethanol Lumpur, ethyl 4-piperidine carboxylic acid, 4-acetamide piperidine, morpholine and the like, among cycloaliphatic amines are preferred.

  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; N, N′-dimethylethylenediamine, N, N′-dimethyl-1,3-propanediamine, N, N′-dimethyl -1,4-butanediamine, N, N′-dimethyl-1,5-pentanediamine, N, N′-dimethyl-1,6-hexanediamine, N, N′-dimethyl-1,7-heptanediamine, Aliphatic alkylenediamines such as N, N′-1,8-octanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butyl Tandiamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butane diamine, branched aliphatic alkylenediamines such as 2,3-dimethyl-1,4-butanediamine; diethylenetriamine, represented by triethylene tetramine, general formula _{NH 2 (CH 2 CH 2 NH} ) , such as tetraethylene pentamine _n H Polyethylene amines; cyclohexane diamine, methyl cyclohexane diamine, isophorone diamine, norbornane dimethyl amine, tricyclodecane dimethyl amine, mensen diamine and other alicyclic diamines; bis (2-methylaminoethyl) ether, 1,2-bis (2-Methylaminoethoxy) ethane, bis [2- (2 Methylaminoethoxy) ethyl] ether, diethylene glycol bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether, 1,4-butanediol bis (3-aminopropyl) ether, 1,2-bis ( Diamines containing ether groups such as 2-aminoethoxy) ethane, 1,1,1-diamino-3,6,9-trioxaundecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane; 1 , Diamines containing heterocyclic amines such as 3-di-4-piperidylpropane; p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, Aromatic diamines such as diaminodiphenylsulfone; benzenetriamine, mela Down, triamines such as 2,4,6-triaminopyrimidine; may be mentioned tetramine of 2,4,5,6-amino pyrimidine, and the like.

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

In addition, it is preferable to select a combination of R ¹ and R ² such that the boiling point of the generated base is 40 ° C. or higher because the handleability at room temperature is improved. When the generated boiling point of the base is not 40 ° C. or higher, when the coating film is formed, particularly the amine produced during drying is likely to evaporate, which may make the operation difficult. Among them, the boiling point of the generated base is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher.

  The base generated from the base generator represented by the chemical formula (1) preferably has one NH group capable of forming an amide bond. When the generated base has two or more NH groups capable of forming an amide bond, the base generator has two or more amide bonds that are cleaved by irradiation with electromagnetic waves and heating, for example, cinnamic acid derivatives Two or more light-absorbing groups such as residues exist in one molecule. In such a case, since the molecular weight is usually increased, there is a problem that the solvent solubility is deteriorated. In addition, when there are two or more light absorbing groups in one molecule, it becomes a base if one amide bond where the light absorbing group and the base are bonded is broken, but a base that still contains the light absorbing group has a large molecular weight. Therefore, the diffusibility is deteriorated, and the sensitivity when used as a base generator is deteriorated. Furthermore, when synthesizing a base generator, if there is one light-absorbing group, it is synthesized by adding an excessive amount of a relatively inexpensive base, but if there are two or more light-absorbing groups, it is relatively expensive. It is necessary to add an excessive amount of the raw material for the light absorbing group. In addition, in the case of a base having two or more NH groups capable of forming an amide bond, there is a problem that purification after synthesis is difficult. In particular, when combined with a polyimide precursor or a polybenzoxazole precursor, it is preferable to have one NH group capable of forming an amide bond.

  On the other hand, when combined with an epoxy compound, the base generated from the base generator represented by the chemical formula (1) is one having two or more NH groups capable of forming an amide bond. It can be suitably used because it can function not only as a curing agent.

In the chemical formula (1), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and may be the same or different. R ³ and R ⁴ are each preferably a hydrogen atom because the cyclization reaction easily proceeds.
On the other hand, in the present invention, in particular, when at least one of R ³ and R ^{4 in} the chemical formula (1) is not hydrogen but is a substituent, compared to the case where both R ³ and R ⁴ are hydrogen. Thus, the base generator of the present invention further improves the solubility in an organic solvent, and improves the affinity with the polymer precursor described later. For example, when at least one of R ³ and R ⁴ is a hydrocarbon group that may have a substituent such as an alkyl group or an aryl group and may contain an unsaturated bond, the solubility in an organic solvent is improves. For example, when at least one of R ³ and R ⁴ is a halogen such as fluorine, the affinity with a polymer precursor containing a halogen such as fluorine is improved. Thus, R ³ and / or R ⁴ can be combined with a desired organic solvent, polymer precursor, or the like to introduce a substituent as appropriate, thereby improving the solubility in the desired organic solvent or the desired polymer. Affinity with the precursor is improved.

The substituent in R ³ and R ⁴ may be the same as the substituent —XR ²⁵ described above. The substituent in R ³ and R ⁴ is usually a monovalent substituent.

In the chemical formula (1), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent, and may be the same or different, and two or more thereof May bond to each other to form a cyclic structure, and may contain a bond of a heteroatom. The substituent in R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same as the substituent -XR ²⁵ described above.
The substituents in R ⁵ , R ⁶ , R ⁷ and R ⁸ are usually monovalent substituents, but may be divalent or higher substituents when forming a cyclic structure to be described later.

In the present invention, it is preferable to introduce one or more substituents into R ⁵ , R ⁶ , R ⁷ and R ⁸ . The wavelength of light to be absorbed can be adjusted by introducing at least one substituent as described above into R ⁵ , R ⁶ , R ⁷ and R ^8. It is also possible to absorb the 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.

  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.

Two or more of R ^{5 to} R ⁸ 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, condensed rings, and heterocyclic rings, and the alicyclic hydrocarbons, condensed rings, and heterocyclic rings. The structure which becomes may be sufficient. For example, R ⁵ to R ⁸ are formed by combining two or more of them, naphthalene share atoms of the benzene ring of R ⁵ to R ⁸ are attached, anthracene, phenanthrene, and fused ring indene You may do it.

As substituents for R ⁵ , R ⁶ , R ⁷ and R ⁸ , halogen atoms (—F, —Cl, —Br, —I), hydroxyl groups, mercapto groups, cyano groups, isocyano groups, nitro groups, nitroso groups, A carboxyl group, a carboxylate group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a hydrocarbon group that may contain the above substituents (hereinafter sometimes referred to as “the above-mentioned hydrocarbon group”), the above substitution A silyl group which may contain a group, an amino group which may contain the above substituent, a methoxy group, an ethoxy group, an isopropyloxy group, a t-butoxy, an ethylhexyloxy group, a cyclohexyloxy group, etc. (—OR ²⁹ , where R ²⁹ is the above-described hydrocarbon group), aryloxy groups such as benzyloxy group and naphthyloxy group (—OAr, where Ar is An aryl group which may have a substituent,), an acyloxy group such as an acetoxy group or a benzoyloxy group (—OCOR ³⁰ , where R ³⁰ is the hydrocarbon group described above), a carbamoyloxy group (—OCONR ³¹ R ³² : R ³¹ and R ³² each independently represent a hydrogen atom or the above-described hydrocarbon group, and may be the same or different, and R ³¹ and R ³² may be bonded to each other, or a cyanooxy group (cyanato) Group) (—OCN), an alkylthio group having 1 to 20 carbon atoms such as a methylthio group and an ethylthio group (—SR ³³ : R ³³ is the above-described hydrocarbon group), an arylthio group such as a phenylthio group and a naphthylthio group (—SAr: Ar is an optionally substituted aryl group), acetylthio group, an acylthio group such as benzoylthio group ^{(-SCOR 34: R} 34 is above the hydrocarbon Group), Shianochio group (thiocyanato group) (- SCN), a formyl group (-COH), acyl group ^{(-COR 35: R 35} is above a hydrocarbon group), an alkoxycarbonyl group ^{(-COOR 36: R 36} is above Hydrocarbon groups), aryloxycarbonyl groups such as benzyloxycarbonyl groups (—COOAr: Ar is an aryl group which may have a substituent), carbamoyl groups (—CONR ³⁷ R ³⁸ : R ³⁷ , R ³⁸ are respectively Independently a hydrogen atom or the above-described hydrocarbon group, which may be the same or different, and R ³⁷ and R ³⁸ may be bonded to each other; a thioacyl group (—CSR ³⁹ : R ³⁹ is the same as that described above; Hydrocarbon group) and alkoxythiocarbonyl group (-CSOR ⁴⁰ : R ⁴⁰ is the above-described hydrocarbon group) are preferable.
Among them, as the substituents for R ⁵ , R ⁶ , R ⁷ and R ⁸ , in particular, from the viewpoint of improving solubility and improving the sensitivity of base generation, a hydroxyl group, a mercapto group, a cyano group, an isocyano group, and the above substituents Hydrocarbon group that may contain, silyl group that may contain the above substituents, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, cyanooxy group (cyanato group), alkylthio group, arylthio group, acylthio group, cyanothio group (Thiocyanato group), formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, thioacyl group, alkoxythiocarbonyl group are preferable, and further hydrocarbon group, alkoxy group, aryl which may contain the above substituents An oxy group, an alkylthio group, and an arylthio group are more preferable.

In chemical formula (1), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and may be the same or different. R ⁹ and R ¹⁰ are each preferably a hydrogen atom because the cyclization reaction easily proceeds.
On the other hand, in the present invention, in particular, when at least one of R ⁹ and R ^{10 in} the chemical formula (1) is not a hydrogen but a substituent, R ⁹ and R are similar to R ³ and R ⁴ described above. Compared with the case where both of ¹⁰ are hydrogen, the base generator of this invention can further improve the solubility with respect to an organic solvent, or can improve the affinity with the polymer precursor mentioned later.

The substituent for R ⁹ and R ¹⁰ may be the same as the above-described substituent —XR ²⁵ . The substituent in R ⁹ and R ¹⁰ is usually a monovalent substituent.

In the chemical formula (1), R ¹¹ is a protective group that can be deprotected only by irradiation with electromagnetic waves. Here, “deprotectable” means that there is a possibility of changing from —OR ¹¹ to —OH. Since “deprotection is possible only by electromagnetic wave irradiation”, there is no need to use a specific component such as acid for deprotection.
By protecting the hydroxy group with a protecting group that can be deprotected only by electromagnetic wave irradiation, the base generator of the present invention does not generate a base only by heating. Further, by appropriately selecting the protective group, compatibility with the polymer precursor to be combined and solubility in the solvent to be used are improved. R ¹¹ is particularly limited as long as it is a protective group for a hydroxy group that can be deprotected only by irradiation with electromagnetic waves under the condition that the amide group present in formula (1) does not decompose in the base generator used in the present invention. It can be used without being used. R ¹¹ 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.

Examples of protecting groups that can be deprotected only by irradiation with electromagnetic waves include acyl groups such as acetyl group, benzoyl group, and acryloyl group using photo-Fries rearrangement reaction; allyl group using photo-Claisen rearrangement reaction, t- A hydrocarbon group such as a butyl group and a phenyl group; represented by the following chemical formula (5) in which an o-nitrobenzyl group and an ester bond and a light absorbing group are bonded via an alkylene chain using a photocleavage reaction. Groups and the like.
As a protecting group that can be deprotected only by irradiation with electromagnetic waves, the group represented by the following chemical formula (5) in which an ester bond and a light absorbing group are bonded via an alkylene chain is used to adjust the absorption wavelength and protect This is preferable because the reaction rate of the group elimination reaction can be adjusted and high sensitivity can be achieved.
Chemical formula (5): —C (═O) —O—R—Ar
(In the chemical formula (5), R represents an alkylene group which may have a substituent, and Ar represents a light-absorbing group).

The alkylene group for R in the chemical formula (5) is not particularly limited. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and an ethylene group or a methylene group is particularly preferable.
The substituent that the alkylene group may have may be the same as the above-described substituent —XR ²⁵ . When it has a substituent, the solubility with respect to an organic solvent improves further, and affinity with a polymer precursor improves. On the other hand, an alkylene group having no substituent is preferred from the viewpoint of the ability to remove the protective group.

Ar in the chemical formula (5) represents a light absorbing group. The light-absorbing group is an atomic group that can absorb at least a part of the irradiated electromagnetic wave.
The light absorbing group in Ar is not particularly limited as long as it absorbs electromagnetic waves and promotes the elimination reaction of the protective group. As such a light absorbing group, for example, an aromatic group which may have a substituent is preferably used. The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. As the carbocyclic ring in the aromatic hydrocarbon group, for example, a condensed polycyclic aromatic hydrocarbon such as a naphthalene ring, a tetralin ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring in addition to a benzene ring; biphenyl, terphenyl, Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have a heteroatom such as O or S in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine. And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like.
Examples of the substituent that the aromatic group may have include those similar to the above-described substituent —XR ²⁵ .

As R ¹¹ , among them, a protective group represented by the following chemical formula (2-1) or the following chemical formula (2-2) is excellent in heat resistance and storage stability, and the elimination reaction due to irradiation with electromagnetic waves is performed. It is preferable from the viewpoint of easy progress.

(In the chemical formula (2-1), R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and may be the same or different. K is 1 or 2. k is 1. In the case of 2, a plurality of R ¹² and a plurality of R ¹³ may be the same or different from each other, and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a substituent. Represents a group, and two or more of them may combine to form a cyclic structure.
In chemical formula (2-2), R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a substituent, and may be the same or different. R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and two or more of R ²⁰ , R ²¹ , R ²² and R ²³ are bonded to form a cyclic structure May be formed. )

R ¹² and R ¹³ in the chemical formula (2-1) and R ¹⁸ and R ¹⁹ in the chemical formula (2-2) each independently represent a hydrogen atom or a substituent, and may be the same or different. May be.
The substituent in R ¹² , R ¹³ , R ¹⁸ and R ¹⁹ may be the same as the above-described substituent —XR ²⁵ . The substituents in R ¹² , R ¹³ , R ¹⁸ and R ¹⁹ are usually monovalent substituents. When R ¹² , R ¹³ , R ¹⁸ or R ¹⁹ has a substituent, the solubility in an organic solvent is further improved, and the affinity with the polymer precursor is improved. On the other hand, from the viewpoint of the ability to remove the protecting group, any one of R ¹² and R ¹³ is preferably a hydrogen atom, more preferably at least one is a hydrogen atom and further has a substituent. In view of the ability to remove the protecting group, both R ¹⁸ and R ¹⁹ are preferably hydrogen atoms.

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ in chemical formula (2-1), and R ²⁰ , R ²¹ , R ²² and R ²³ in chemical formula (2-2) are each independently a hydrogen atom, or Represents a substituent, and two or more of them may combine to form a cyclic structure.
R ^{14 to} R ¹⁷ and R ^{20 to} R ²³ can be the same as those in R ⁵ , R ⁶ , R ⁷ and R ⁸ .
By introducing at least one substituent into R ^{14 to} R ¹⁷ and R ^{20 to} R ²³ , the wavelength of light to be absorbed can be adjusted, and a desired wavelength is absorbed by introducing a substituent. It can also be made to do. 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 desorption ability in consideration of the absorption wavelength of the polymer precursor to be combined.

Among them, R ¹⁴ and R ¹⁵ are a hydroxyl group, a mercapto group, a cyano group, an isocyano group, a hydrocarbon group that may contain the above substituent, a silyl group that may contain the above substituent, an alkoxy group, from the point of increasing sensitivity. Aryloxy group, acyloxy group, carbamoyloxy group, cyanooxy group (cyanato group), alkylthio group, arylthio group, acylthio group, cyanothio group (thiocyanato group), formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Group, a thioacyl group, and an alkoxythiocarbonyl group are preferable, and a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group that may contain the above substituents are more preferable.
R ²¹ is preferably halogen from the viewpoint of high sensitivity.
R ²² represents a hydroxyl group, a mercapto group, a cyano group, an isocyano group, a hydrocarbon group that may contain the above substituent, a silyl group that may contain the above substituent, an alkoxy group, an aryloxy group from the viewpoint of increasing sensitivity. , Acyloxy group, carbamoyloxy group, cyanooxy group (cyanato group), alkylthio group, arylthio group, acylthio group, cyanothio group (thiocyanato group), formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, thioacyl Group, an alkoxythiocarbonyl group is preferable, and a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group that may contain the above substituents are more preferable.
In particular, when R ²¹ is a bromine atom and R ²² is a hydroxyl group, the pKa of the hydroxyl group is adjusted by the adjacent bromine atom, which is preferable.

In the chemical formula (2-2), R ²⁴ represents a hydrogen atom or a substituent. The substituent for R ²⁴ may be the same as the above-described substituent —XR ²⁵ .

In the above chemical formula (1), m and n each represent the number of repeating units, m is an integer of 0 or more, n is an integer of 0 or more, provided that m + n is an integer of 1 or more. Since an amine is generated when a hydroxyl group and a carbonyl group react both within and between molecules, the upper limits of m and n are not particularly limited. From the viewpoint of reaction efficiency, m and n are each preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. Further, m + n is preferably 10 or less, and more preferably 5 or less.
Among these, when m + n is an integer of 1 to 3, it is preferable from the viewpoint that the intramolecular cyclization reaction is facilitated by heating and the generation efficiency of the base is improved.

  The base generator represented by the chemical formula (1) of the present invention needs to absorb at least a part of the exposure wavelength in order for the deprotection reaction to proceed. The wavelength of a high-pressure mercury lamp that is a general exposure light source includes 365 nm, 405 nm, and 436 nm. For this reason, it is preferable that the base generator represented by the chemical formula (1) of the present invention absorbs at least one electromagnetic wave having a wavelength of 365 nm, 405 nm, or 436 nm. In such a case, it is preferable because the number of applicable polymer precursors is further increased.

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

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

  When the base generator represented by the chemical formula (1) is used, the protective group is first deprotected by irradiation with electromagnetic waves. The wavelength and irradiation amount of the electromagnetic wave used for deprotecting the protecting group are appropriately adjusted depending on the absorption wavelength of the base generator, the polymer precursor used in combination, and the like, and are not particularly limited.

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

  The base generator represented by the chemical formula (1) is a polymer precursor used in combination and / or any of the solvents listed as solvents that dissolve, disperse, or dilute the photosensitive resin composition described below. On the other hand, the saturation solubility at 25 ° C. is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The base generator represented by the chemical formula (1) includes, among others, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, aromatic hydrocarbon solvents such as toluene, and propylene glycol mono Saturation at 25 ° C. of at least one solvent selected from the group consisting of glycol monoethers such as ethyl ether (so-called cellosolves), amides such as N, N-dimethylformamide, and mixed solvents composed of these solvents The solubility is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. When the polymer precursor used in combination and / or the solvent that is a good solvent for the polymer precursor has good solvent solubility as described above, a sufficient amount of the base generator of the present invention is used. Therefore, the photosensitive resin composition can sufficiently exhibit a catalytic function and has good storage stability.

  Especially, it is preferable that the saturation solubility in 25 degreeC is 0.1 mass% or more with respect to the polymer precursor used in combination, and it is still more preferable that it is 0.5 mass% or more. Thus, when it is compatible with the compound, it is not necessary to use a solvent, and the process of drying the solvent can be omitted, so that it can be used in a wide range of fields.

As a method for synthesizing the base generator represented by the chemical formula (1) of the present invention, for example, it can be synthesized with reference to Non-Patent Document 2, Synthesis, (4), 306-8;
Specifically, it can be obtained by ring-opening addition of a desired amine (NHR ¹ R ² ) to phthalide, isochromanone or the like, and then adding a desired protective group to introduce a protective group into the hydroxy group.

As a method for introducing a protecting group, for example, when the protecting group is an allyl group, for example, an allyl halide such as Br—CH ₂ —CH═CH ₂ is used in the presence of a strong base such as sodium hydride. And reacting with a hydroxyl group.
For example, when the protecting group is an o-nitrobenzyl group, a halide such as 2-nitrobenzyl chloride is used and reacted with a hydroxyl group in the presence of a strong base such as sodium hydride.
Further, for example, when the protecting group is a group represented by the above chemical formula (5), for example, using a carbonate acid chloride of the chemical formula (5), in the presence of a base such as pyridine or triethylamine, a hydroxyl group And reacting.

The base generator represented by the chemical formula (1) according to the present invention generates a base by further heating after irradiation with electromagnetic waves, so that it has excellent storage stability and can be applied in various ways. is there. A base such as an acid-base indicator, not limited to combining with a polymer precursor whose reaction to the final product is promoted by heating in the presence of a basic substance or in the presence of a basic substance, which will be described in detail later Thus, various photosensitive compositions can be formed in combination with a compound whose structure and physical properties change. Such photosensitive compositions can be used for paints, printing inks, sealing agents, or adhesives, display devices, semiconductor devices, electronic components, micro electro mechanical systems (MEMS), optical members, or architecture. It can be used as a material forming material.
For example, in an image forming medium formed by coating or impregnating a base material with an image forming layer containing at least a base generator and an acid-base indicator, when the image forming layer is exposed, the base generator is The present invention can also be applied to a display device such as an image forming medium in which an image is formed by generating a base that reacts with an acid-base indicator.

<Photosensitive resin composition>
The photosensitive resin composition according to the present invention is represented by a polymer precursor whose reaction to the final product is accelerated by a basic substance or by heating in the presence of the basic substance, and represented by the following chemical formula (1): And a base generator that generates a base by irradiation with electromagnetic waves and heating.
(In the chemical formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group that may contain a substituent, and may be the same or different, and R ¹ and R ² there bound good .R ³ and R ⁴ may form a cyclic structure each independently represent a hydrogen atom or a substituent, good .R ³ and R ⁴ be different even in the same A plurality of R ^{3 s} and a plurality of R ^{4 s} may be the same or different from each other, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, or Represents a substituent, and two or more of them may combine to form a cyclic structure, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and may be the same or different. If which may be .R ⁹ and ^{R 10} are a plurality, a plurality of ^{R 9} Judges, and plural R ¹⁰ together are optionally being the same or different .R ¹¹ is only the irradiation of the electromagnetic wave is a protective group which can be deprotected .m and n represents the number of repeating units, respectively, m is an integer of 0 or more, n is an integer of 0 or more, provided that m + n is an integer of 1 or more.)

  Since the photosensitive resin composition according to the present invention contains the base generator according to the present invention, the types of polymer precursors that can be combined can be increased, the storage stability is excellent, and the reliability is higher. High cured film can be obtained, and the heat resistance and stability of the final product are also 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. The following are typical examples, but the invention is not limited to these.

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

Examples of the compound that has a reactive substituent and undergoes a polymerization reaction include compounds having one or more epoxy groups, compounds having one or more oxetane groups, and compounds 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, use a compound having a functional group having reactivity with the epoxy group. May be. Examples of the compound having a functional group having reactivity with an epoxy group include a compound having a carboxyl group, a phenolic hydroxyl group, a mercapto group, or a primary or secondary aromatic amino group. It is 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, film strength is lowered and tackiness is caused on the surface of the cured film, which may cause impurities and the like to easily 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, YDFN series, YDB series by Toto Kasei Co., Ltd., Denacol series by Nagase ChemteX, Epolite series by Kyoeisha Chemical Co., Ltd. Although's etc. but the invention is not limited thereto. Two or more of these epoxy resins may be used in combination. Among these, bisphenol-type epoxy resins are preferable because grades having different molecular weights are widely available as compared with other various epoxy compounds, and adhesiveness and reactivity can be arbitrarily set.

The compound having a carboxyl group which may be used in combination preferably has a phthalic anhydride skeleton which may be hydrogenated. Examples of the acid anhydride include methyltetrahydrophthalic anhydride (Me-THPA) (Quinhard 200 (Nippon Zeon), HN-2200 (Hitachi Chemical Co., Ltd.), Ricacid MT-500 (New Nippon Rika)), methyl hexahydrophthalic anhydride Acid (Me-HHPA) (Quinhard 500 (Nippon Zeon), HN-5500 (Hitachi Chemical Co., Ltd.), Ricacid MH-700 (New Nippon Rika)), Methyl nadic anhydride (25) (MHAC-P (Hitachi Chemical Industry)) , Hydrogenated methyl nadic acid (26) (HNA (New Nippon Rika)), alkyl-modified acid anhydride (27) (Epicure YH-306, Epicure YH-307 (Japan Epoxy Resin)) and the like.
As the compound having a phenolic hydroxyl group, compounds having two or more phenolic hydroxyl groups in one molecule are preferably used, and the molecular weight and molecular structure thereof are not particularly limited. For example, phenol novolak resin, phenol Aralkyl resin, cresol novolak resin, tert-butylphenol novolak resin, novolak type phenol resin such as nonylphenol novolak resin, resol type phenol resin, polyoxystyrene such as polyparaoxystyrene, dicyclopentadiene modified phenol resin, terpene modified phenol resin, tri A phenol methane type resin etc. are mentioned, A phenol resin can be used individually or in combination of 2 or more types.
As the compound having a mercapto group (-SH group), a compound having two or more mercapto groups in one molecule is preferably used, and conventionally known compounds can be used. Those having three or more mercapto groups in one molecule are more preferable. In addition, the compound which has a mercapto group is known by the name of thiol.
Examples of the compound having a mercapto group include 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3,5-triazine-2,4, 6-trithiol (trimercapto-triazine), 1,5-naphthalenedithiol, trithioglycerin, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), trimethylolpropane tristhioglycolate , Trimethylolpropane tristhiopropionate, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 2,4,6-tris (mercaptomethyl) mesitylene, tris (Mercaptomethyl) isocyanurate, tris (3-mercapto (Lopyl) isocyanurate, 2,4,5-tris (mercaptomethyl) -1,3-dithiolane, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, 1,2,4,5-tetrakis (mercaptomethyl) ) Benzene, tetramercaptobutane, pentaerythritol.

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

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

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

(Polysiloxane precursor)
Examples of the compound that undergoes hydrolysis and polycondensation between molecules include polysiloxane precursors.
As the polysiloxane precursor, Y _n SiX _(4-n) (wherein Y represents an alkyl group, fluoroalkyl group, vinyl group, phenyl group, or hydrogen which may have a substituent, A hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen, where n is an integer from 0 to 3. And the hydrolyzed polycondensate of the organosilicon compound. Among these, those in which n is 0 to 2 in the above formula are preferable. 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.

(Polyimide precursor)
As a polyimide precursor, the polyamic acid which has a repeating unit represented by following Chemical formula (6) is used suitably.

(In the chemical formula (6), R ⁴¹ is a tetravalent organic group. R ⁴² is a divalent organic group. R ⁴³ and R ⁴⁴ are a hydrogen atom or an organic group. N is 1 or more. It is a natural number.)

Examples of the case where R ⁴³ and R ⁴⁴ are an organic group include 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 (6 ') is preferably used from the viewpoint of alkali developability.

(In the chemical formula (6 ′), R ⁴¹ is a tetravalent organic group. R ⁴² is a divalent organic group. N is a natural number of 1 or more.)

In the formulas (6) and (6 ′), the tetravalent R ⁴¹ represents a tetracarboxylic acid residue derived from an acid dianhydride or the like, and the divalent R ⁴² represents a diamine residue. Incidentally, tetravalent R ⁴¹ represents only valence for bonding with the acid, but may have further substituents other. Similarly, the divalent value of R ⁴² 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 (6 ′), R ⁴¹ or R ⁴² is preferably an aromatic compound, and R ⁴¹ and R ⁴² are more preferably aromatic compounds. At this time, in R ⁴¹ of the chemical formula (6 ′), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ⁴¹ may be bonded to the same aromatic ring. It may be bonded to different aromatic rings. Similarly, in R ⁴² of the chemical formula (6 ′), two groups ((—NH—) ₂ ) bonded to R ⁴² may be bonded to the same aromatic ring, and may be bonded to different aromatic rings. It may be combined.

  The polyamic acid 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.

  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.

  The acid dianhydride applicable to the reaction for obtaining the polyimide precursor of the present invention is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diacids described in paragraphs 0123 to 0124 of JP2011-068888A. Acid dianhydrides such as anhydrides and aromatic tetracarboxylic dianhydrides can be used. 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. For example, diamine components such as aromatic amines, aliphatic amines, alicyclic diamines, and guanamines described in paragraphs 0126 to 0137 of JP2011-068888A can be used. . A particularly preferred diamine component is an aromatic diamine, such as p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, benzidine, 2,2 ′. -Dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl and the like.
Here, the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance. However, depending on the desired physical properties, the diamine may be an aliphatic diamine or siloxane within a range not exceeding 60 mol%, preferably not exceeding 40 mol%. Non-aromatic diamines such as diamines may be used.

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

<Polybenzoxazole precursor>
As the polybenzoxazole precursor used in the present invention, a polyamide alcohol having a repeating unit represented by the following chemical formula (8) is suitably used.

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

(In the chemical formula (8), R ⁴⁵ is a divalent organic group. R ⁴⁶ is a tetravalent organic group. N is a natural number of 1 or more.)

In addition, although the divalent value of R ⁴⁵ indicates only the valence for bonding with an acid, it may have another substituent. Similarly, the tetravalent value of R ⁴⁶ indicates only the valency for bonding to the amine and hydroxyl groups, but may have other substituents.

The polyamide alcohol having a repeating unit represented by the chemical formula (8) gives an excellent heat resistance and dimensional stability to the finally obtained polybenzoxazole. In the chemical formula (8), R ⁴⁵ or R ⁴⁶ is preferably an aromatic compound, and R ⁴⁵ and R ⁴⁶ are more preferably aromatic compounds. At this time, in R ⁴⁵ of the chemical formula (8), two groups (—CO—) ₂ bonded to R ⁴⁵ may be bonded to the same aromatic ring or bonded to different aromatic rings. May be. Similarly, in R ⁴⁶ of the chemical formula (8), four groups ((—NH—) ₂ (—OH) ₂ ) bonded to R ⁴⁶ may be bonded to the same aromatic ring, It may be bonded to different aromatic rings.

  The polyamide alcohol represented by the chemical formula (8) 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 applicable to the reaction for obtaining the polybenzoxazole precursor and derivatives thereof include, for example, dicarboxylic acids such as phthalic acid described in paragraph 0146 of JP2011-068888A, or acid halides thereof. And active ester forms with hydroxybenzotriazole and the like, but are not limited thereto. These may be used alone or in combination of two or more.

  Specific examples of hydroxydiamine include, but are not limited to, hydroxydiamine such as 3,3'-dihydroxybenzidine described in paragraph 0146 of JP2011-068888A. These may be used alone or in combination of two or more.

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

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

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

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

  In addition, the solvent at the time of a polyimide precursor and a polybenzoxazole precursor synthesis | combination is a polar solvent, and may be the same as that of the paragraph 0152 of Unexamined-Japanese-Patent No. 2011-068888. Typical examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, and these solvents are used alone or in combination of two or more.

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

<Other ingredients>
The photosensitive resin composition according to the present invention may be a simple mixture of the base generator represented by the chemical formula (1), one or more kinds of polymer precursors, and a solvent. Or other components such as thermosetting component, non-polymerizable binder resin other than polymer precursor, other photosensitive component that generates acid or base by light, base proliferating agent, sensitizer, etc. An adhesive resin composition may be prepared. Examples of these other components include the same components as those described in paragraphs 0158 to 0163 of JP2011-068888A.

  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.

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

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

In the photosensitive resin composition according to the present invention, the polymer precursor (solid content) is usually 50.1 to 99.9% by weight, further 62.5% based on the entire solid content of the photosensitive resin composition. It is preferably ˜99.5% by weight. The base generator represented by the chemical formula (1) is usually 0.1 to 49.9% by weight, more preferably 0.5 to 37.5% by weight, based on the entire solid content of the photosensitive resin composition. It is preferable that
In addition, solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

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

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

  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.

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

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

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

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

  The photosensitive resin composition of the present invention includes propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. After being dissolved in a polar solvent such as toluene, aromatic hydrocarbons such as toluene, and a mixed solvent composed of these solvents, immersion method, spray method, flexographic printing method, gravure printing method, screen printing method, spin coating method, Apply to the surface of the substrate such as silicon wafer, metal substrate, ceramic substrate, resin film, etc. by dispensing method and heat to remove most of the solvent to give a non-sticky coating on the substrate surface Can do. 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.

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

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

(Developer)
The developer used in the development step is not particularly limited as long as the solvent that changes the solubility of the irradiation site is used as the developer. 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” means “parts by mass” unless otherwise specified. The produced base generator was confirmed in chemical structure by ¹ H NMR measurement.
Moreover, each measurement and experiment were performed using the apparatus shown below.
¹ H NMR measurement: JEOL JNM-LA400WB, manufactured by JEOL Ltd.
Manual exposure: manufactured by Dainippon Kaken, MA-1100
Absorbance measurement: UV-2550 manufactured by Shimadzu Corporation, UV-visible spectrophotometer
5% mass reduction temperature measurement: manufactured by Shimadzu Corporation, differential thermal / thermal mass simultaneous measurement device DTG-60

(Production Example 1: Synthesis of base generator (1))
Synthesis, (4), 306-8; 1991, [2- (hydroxymethyl) phenyl] -1-piperidyl-methanone was synthesized. [2- (hydroxymethyl) phenyl] -1-piperidyl-methanone 0.5 g (2.3 mmol), 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) in a 50 mL flask under a nitrogen atmosphere and in an ice bath ) 562 mg (4.6 mmol, 2.0 eq) was dissolved in 10 ml of chloroform, and 700 mg (2.5 mmol, 1.1 eq) of 4,5-dimethoxy-2-nitrobenzyl chloroformate (Aldrich) was slowly added. , Stirred overnight. After completion of the reaction, water was added, and the chloroform layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, concentrated and then subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate 10/1 to 0). / 1 (volume ratio)) to obtain 0.21 g of a base generator (1) represented by the following chemical formula (9).

(Production Example 2: Synthesis of base generator (2))
Org. Lett., 2003, 5 (25), pp 4867-4870, 6-bromo-7-methoxymethoxycoumarin-4-ylmethoxycarbonyl chloroformate was synthesized. In Production Example 1, by using 6-bromo-7-methoxymethoxycoumarin-4-ylmethoxycarbonyl chloroformate instead of 4,5-dimethoxy-2-nitrobenzyl chloroformate, (6-bromo- 0.12 g of 7- (methoxymethoxy) -2-oxo-2H-chromen-4-yl) methyl 2- (piperidine-1-carbonyl) benzyl carbonate was obtained. In a 10 ml flask, 0.10 g of (6-bromo-7- (methoxymethoxy) -2-oxo-2H-chromen-4-yl) methyl 2- (piperidine-1-carbonyl) benzyl carbonate was added to trifluoroacetic acid (Kanto Chemical). The product was dissolved in 2 ml, and stirred at room temperature for 15 minutes, and then trifluoroacetic acid was removed under vacuum to obtain 60 mg of a base generator (2) represented by the following chemical formula (10).

(Comparative Production Example 1: Synthesis of Comparative Base Generator (1))
In a 100 mL flask under a nitrogen atmosphere and an ice bath, 0.8 g (6.2 mmol) of aluminum chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 12 mL of chloroform, and triethylamine (Tokyo Chemical Industry Co., Ltd.) 1. 4 mL was added slowly. In a 50 mL flask under nitrogen atmosphere, 0.24 mL (2.9 mmol) of pyrrolidine (Tokyo Chemical Industry Co., Ltd.) and 1.0 g (7.4 mmol) of phthalide (Tokyo Chemical Industry Co., Ltd.) are dissolved in 6 mL of chloroform. And slowly added to the 100 mL flask described above and stirred at room temperature for 4 days. After completion of the reaction, water was added, and the chloroform layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, concentrated and then subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate 10/1 to 0). / 1 (volume ratio)) to obtain 0.18 g of a comparative base generator (1) represented by the following chemical formula (11).

(Comparative Production Example 2: Synthesis of Comparative Base Generator (2))
According to Journal of photopolymer science and technology, 20, 2, 299-302, a comparative base generator (2) represented by the following chemical formula (12) was synthesized.

<Evaluation of base generator>
The base generator (1) obtained in Production Example 1 was evaluated by measuring the molar extinction coefficient and the 5% weight loss temperature.
(1) Molar extinction coefficient The base generator (1) was dissolved in acetonitrile at a concentration of 1 × 10 ⁻⁴ mol / L, the solution was filled in a quartz cell (optical path length 10 mm), 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. The results are shown in Table 1.

(2) 5% weight reduction temperature In order to evaluate the heat resistance of the base generator (1), a 5% weight reduction temperature was measured under the condition of a heating rate of 10 ° C / min. The results are shown in Table 1.

(3) Base generation ability The i-line sensitivity was evaluated using NMR measurement. In addition, i-line sensitivity is the exposure amount in i-line conversion required when 50% deprotection reaction proceeds.
Regarding the base generator (1), 1 mg of a sample was dissolved in 0.5 mL of heavy dimethyl sulfoxide in a quartz NMR tube.
Using a base generator (1), a filter that cuts light of 350 nm or less (trade name: GG385, thickness: 1 mm, manufactured by Shibuya Optical Co., Ltd.) and a high-pressure mercury lamp, light irradiation is performed intermittently, and ¹ H NMR Was measured, the proportion of the deprotection reaction was measured, and the irradiation amount at which the deprotection rate was 50% was determined. The deprotection rate was 50% when 60 J / cm ² was irradiated.
The sample in which the 50% deprotection reaction had progressed was heated at 160 ° C. for 10 minutes, and ¹ H NMR was measured. As a result, it was confirmed that phthalide and piperidine were produced.

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

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

(Creation of coating film)
The photosensitive resin composition (1) of Example 1 was spin-coated on a chrome-plated glass so as to have a final film thickness of 4.0 μm, and dried on a hot plate at 100 ° C. for 10 minutes. One coating film of the resin composition (1) was obtained. The exposure was carried out in a pattern with a high-pressure mercury lamp using a manual exposure machine. Then, it heated at 155 degreeC for 10 minute (s). The heated coating film was immersed in a 9: 1 mixed solution of 2.38 wt% tetramethylammonium hydroxide and isopropanol. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, it was heated at 350 ° C. for 1 hour to perform imidization. From this result, it became clear that the photosensitive resin composition of the present invention can form a good pattern.

(Example 2: Preparation of photosensitive resin composition (2))
In Example 1, a photosensitive resin composition (2) was prepared in the same manner as in Example 1 except that the base generator (2) was used instead of the base generator (1).
When the coating film was produced and the pattern was formed like Example 1 using the photosensitive resin composition (2), it became clear that a favorable pattern can be formed.

(Comparative Example 1: Preparation of comparative resin composition (1))
A comparative resin composition (1) having the following composition was prepared.
Polyimide precursor (1): 100 parts by weight Comparative base generator (1): 15 parts by weight Solvent (NMP (N-methylpyrrolidone)): 843 parts by weight Using the comparative resin composition (1) When a coating film was prepared and a pattern was formed in the same manner as in Example 1, the pattern could not be formed because the comparative base generator (1) did not have photosensitivity.

(Comparative Example 2: Preparation of comparative photosensitive resin composition (2))
A comparative photosensitive resin composition (2) having the composition shown below was prepared.
Polyimide precursor (1): 100 parts by weight Comparative base generator (2): 15 parts by weight Photoacid generator (N-trifluoromethanesulfonyloxy-1,8-naphthylimide, Midori Chemical Co., Ltd.): 1 part by weight / solvent (NMP (N-methylpyrrolidone)): 843 parts by weight Using the comparative photosensitive resin composition (2), a coating film was prepared and a pattern was formed in the same manner as in Example 1. The pattern could not be formed. In the comparative photosensitive resin composition (2), it is presumed that the tetrahydropyranyl group of the comparative base generator (2) was eliminated by the carboxyl group contained in the polyimide precursor used as the resin, and the photosensitive function was lost.

(Examples 3 to 4: Preparation of photosensitive resin compositions (3) to (4))
Using the base generator (1) or (2) according to the present invention, photosensitive resin compositions (3) and (4) having the following compositions were prepared.
Epoxy resin (Marpeloop G01100, NOF Corporation): 100 parts by weight Base generator (1) or (2): 15 parts by weight Solvent (N-methyl-2-pyrrolidone): 230 parts by weight

Each of the photosensitive resin compositions (3) and (4) was spin-coated on a chrome-plated glass so as to have a final film thickness of 0.5 μm, and dried on an 80 ° C. hot plate for 15 minutes. Two coating films of each photosensitive resin composition were obtained. About 1 sheet of the coating film of each photosensitive resin composition, 1 J / cm < ² > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Then, about each coating film, it heated for 30 minutes at 160 degreeC as heating which respond | corresponds to baking after exposure (PEB). When the heated coating film was immersed in a chloroform solution at room temperature for 10 minutes, it was revealed that the two sheets heated after exposure did not dissolve in the mixed solution and the epoxy resin was cured. On the other hand, about 2 sheets heated without exposure, it melt | dissolved in the said mixed solution.

The photosensitive resin compositions (3) and (4) were applied onto a chromium-plated non-alkali glass chromium surface and dried in an oven at 80 ° C. for 10 minutes.
The coating film was exposed with a high-pressure mercury lamp so that the integrated light amount was 10 J / cm ² and stored at room temperature for 1 hour, and then an alkali-free glass was brought into close contact with the coating film surface of the sample at 150 ° C. for 1 hour. And heated in an oven.
As a result, the chromium-free alkali-free glass and alkali-free glass were completely bonded by the cured product of the photosensitive resin composition 1 and could not be peeled off.
From the above, when the base generator according to the present invention is used, a base is not generated only by light irradiation, so that the pot life is increased, that is, after a predetermined time has elapsed after light irradiation, the substrates are bonded together, etc. It became clear that this work would be possible.

(Comparative Example 3: Preparation of comparative photosensitive resin composition (3))
A comparative photosensitive resin composition (3) having the following composition was prepared using the comparative base generator (2).
-Epoxy resin (Madeloop G01100 manufactured by NOF Corporation): 100 parts by weight-Comparative base generator (2): 15 parts by weight-Photoacid generator (N-trifluoromethanesulfonyloxy-1,8-naphthylimide, Midori Chemical Co., Ltd.): 1 part by weight / solvent (N-methyl-2-pyrrolidone): 230 parts by weight The comparative photosensitive resin composition (3) was applied onto a chromium-free non-alkali glass chrome surface at 80 ° C. In the oven for 10 minutes.
The coating was exposed with a high-pressure mercury lamp so that the integrated light intensity was 10 J / cm ² , then stored at room temperature for 1 hour, and then an alkali-free glass was adhered to the coating surface of the sample, but the resin was already cured. Therefore, it was impossible to bond alkali-free glass.

Claims (7)

A base generator that is represented by the following chemical formula (1) and generates a base upon irradiation and heating of electromagnetic waves.
(In the chemical formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group that may contain a substituent, and may be the same or different, and R ¹ and R ² May combine to form a cyclic structure, provided that at least one of R ¹ and R ² is a hydrocarbon group which may contain a substituent, and R ³ and R ⁴ are each independently hydrogen Represents an atom or a substituent, and may be the same or different, and when there are a plurality of R ³ and R ⁴ , a plurality of R ³ and a plurality of R ⁴ may be the same or different from each other; which may be .R ^{5, R 6, R 7} and R ⁸ each independently represent a hydrogen atom or a substituent, those two or more are combined to optionally form a cyclic structure .R ⁹ And R ¹⁰ is a hydrogen atom , and R ¹¹ is removed only by electromagnetic wave irradiation. (Protective group which can be protected. M and n each represent the number of repeating units, m is 1 and n is 0. ) The base generator according to claim 1 , wherein in the chemical formula (1), R ¹¹ is a protecting group represented by the following chemical formula (2-1) or the following chemical formula (2-2).
(In the chemical formula (2-1), R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and may be the same or different. K is 1 or 2. k is 1. In the case of 2, a plurality of R ¹² and a plurality of R ¹³ may be the same or different from each other, and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a substituent. Represents a group, and two or more of them may combine to form a cyclic structure.
In chemical formula (2-2), R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a substituent, and may be the same or different. R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and two or more of R ²⁰ , R ²¹ , R ²² and R ²³ are bonded to form a cyclic structure May be formed. ) A polymer precursor whose reaction to the final product is accelerated by heating in the presence of a basic substance or in the presence of a basic substance, and a base expressed by the following chemical formula (1) and irradiated with electromagnetic waves and heated The photosensitive resin composition containing the base generator which generate | occur | produces.
(In the chemical formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group that may contain a substituent, and may be the same or different, and R ¹ and R ² May combine to form a cyclic structure, provided that at least one of R ¹ and R ² is a hydrocarbon group which may contain a substituent, and R ³ and R ⁴ are each independently hydrogen Represents an atom or a substituent, and may be the same or different, and when there are a plurality of R ³ and R ⁴ , a plurality of R ³ and a plurality of R ⁴ may be the same or different from each other; which may be .R ^{5, R 6, R 7} and R ⁸ each independently represent a hydrogen atom or a substituent, those two or more are combined to optionally form a cyclic structure .R ⁹ And R ¹⁰ is a hydrogen atom , and R ¹¹ is removed only by electromagnetic wave irradiation. (Protective group which can be protected. M and n each represent the number of repeating units, m is 1 and n is 0. ) 4. The photosensitive resin according to claim 3 , wherein in the chemical formula (1) of the base generator, R ¹¹ is a protecting group represented by the following chemical formula (2-1) or the following chemical formula (2-2). Composition.
(In the chemical formula (2-1), R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and may be the same or different. K is 1 or 2. k is 1. In the case of 2, a plurality of R ¹² and a plurality of R ¹³ may be the same or different from each other, and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a substituent. Represents a group, and two or more of them may combine to form a cyclic structure.
In chemical formula (2-2), R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a substituent, and may be the same or different. R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, and two or more of R ²⁰ , R ²¹ , R ²² and R ²³ are bonded to form a cyclic structure May be formed. ) The polymer precursor is one selected from the group consisting of compounds and polymers having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzoxazole precursor The photosensitive resin composition of Claim 3 or 4 containing the above. The pattern forming material which consists of the photosensitive resin composition as described in any one of the said Claims 3 thru | or 5 . A coating film or a formed body is formed using the photosensitive resin composition according to any one of claims 3 to 5 , and the coating film or the formed body is irradiated with electromagnetic waves in a predetermined pattern, and after irradiation. Alternatively, a method for producing a relief pattern is characterized in that development is carried out after heating at the same time as irradiation to change the solubility of the irradiated portion.