WO2017141734A1 - Photosensitive resin composition, dry film, cured product, printed circuit board, and photobase generator - Google Patents

Abstract

Provided are a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the dry film resin layer, a printed circuit board having the cured product, and a photobase generator having excellent sensitivity. The photosensitive resin composition and the like are characterized in comprising an ion-type photobase generator that contains a carboxylic acid and a base and is represented by general formula (1). (In formula (1), R₁ through R₄ and X₁ and X₂ are each independently a hydrogen atom or substitution group, at least one of X₁ and X₂ is an electron-attracting group, Y is an electron-releasing group, and B is a base.)

Description

Photosensitive resin composition, dry film, cured product, printed wiring board, and photobase generator

The present invention relates to a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a photobase generator.

A method of chemically modifying a resin using a photobase generator that generates a base by the action of light as a catalyst has been applied to the fields of photoresist materials and photocuring materials. For example, Patent Document 1 contains a photobase generator composed of a salt of a carboxylic acid that is photodecarboxylated and a tertiary amine, and a polyimide precursor and / or a polybenzoxazole precursor. A functional resin composition is described.

Japanese Patent No. 4830435

There is a demand for improvement in the sensitivity of photosensitive resin compositions containing a photobase generator. If sensitivity is improved, patterning can be performed with good resolution even if reaction conditions such as light irradiation conditions for generating bases and heat treatment conditions when using bases for thermal curing are relaxed. There is expected. In addition, if the sensitivity is improved, the range of selection of the reaction conditions as described above is expanded, and the heat resistance of other components such as the base material on which the photosensitive resin composition is applied, and other components in the photosensitive resin composition. It is expected that optimum reaction conditions can be selected compared to the conventional ones in consideration of characteristics such as properties. However, the photobase generator composed of a salt of a carboxylic acid and a tertiary amine that performs photodecarboxylation described in Patent Document 1 cannot provide sufficient sensitivity.

Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a print having the cured product. It is to provide a wiring board and a photobase generator excellent in sensitivity.

As a result of intensive studies in view of the above, the present inventors have found that the above problem can be solved by using a compound having a specific structure as a photobase generator, and have completed the present invention.

That is, the photosensitive resin composition of the present invention is characterized by containing an ionic photobase generator of carboxylic acid and base represented by the following general formula (1).

(In the formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, and at least one of X ₁ and X ₂ is an electron-withdrawing group; Is an electron donating group, and B is a base.)

In the photosensitive resin composition of the present invention, the photoabsorber preferably has a molar extinction coefficient of 300 L · mol ⁻¹ · cm ⁻¹ or more.

In the photosensitive resin composition of the present invention, in the general formula (1), the electron attractive group is —C≡N, —NO ₂ , —COCH ₃ , —F, —Cl, —Br, and —I. Preferably it is selected from the group consisting of

In the photosensitive resin composition of the present invention, in the general formula (1), the electron donating group is —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , —C (CH ₃ ) ₃ , It is preferably selected from the group consisting of —C ₆ H ₅ , —OH, —OCH ₃ , and —OC ₆ H ₅ .

The photosensitive resin composition of the present invention preferably further contains a polymer precursor.

In the photosensitive resin composition of the present invention, the polymer precursor is preferably at least one of polyamic acid and polyamic acid ester.

In the photosensitive resin composition of the present invention, the polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).

(In formula (4-1), R ₇ is a tetravalent organic group, R ₈ is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene. R _9-1 and R _10-1 may be the same or different from each other, and may be a monovalent organic group or a functional group having silicon, and R ₁₁ may be a divalent organic group. M is an integer of 1 or more, and n is 0 or an integer of 1 or more.)

In the photosensitive resin composition of the present invention, R ₇ in the general formula (4-1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an aliphatic group. A tetravalent organic group containing a cyclic hydrocarbon group or a tetravalent organic group containing a fluorine atom is preferable.

The photosensitive resin composition of the present invention is a polyamic acid ester in which the polymer precursor has a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2): It is preferable that

(In the formula (4-1-1), R ₈ is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R _{9 -1} and R _10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)

(In the formula (4-1-2), R ₈ is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R _{9 -1} and R _10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)

The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.

The cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.

The printed wiring board of the present invention is characterized by having the cured product.

The photobase generator of the present invention is an ionic type of a carboxylic acid and a base represented by the following general formula (1).

(In the formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, and at least one of X ₁ and X ₂ is an electron-withdrawing group; Is an electron donating group, and B is a base.)

In the photobase generator of the present invention, in the general formula (1), the electron-withdrawing group is represented by —C≡N, —COCH ₃ , —NO ₂ , —F, —Cl, —Br, and —I. Preferably there is.

In the photobase generator of the present invention, in the general formula (1), the electron donating group is —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , —C (CH ₃ ) ₃ , — C ₆ H ₅ , —OH, —OCH ₃ , and —OC ₆ H ₅ are preferred.

According to the present invention, a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring having the cured product A photobase generator excellent in plate and sensitivity can be provided.

2 is a chart showing the ¹ H-NMR spectrum of the photobase generator MONPA-TBD synthesized in Example 1-1. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm). 2 is a chart showing the ¹ H-NMR spectrum of the photobase generator MONPA-DBU synthesized in Example 1-2. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm). 2 is a chart showing the ¹ H-NMR spectrum of the photobase generator MONPA-2E4MZ synthesized in Example 1-3. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm). 2 is a chart showing the ¹ H-NMR spectrum of the photobase generator MONPA-DBA synthesized in Example 1-4. The horizontal axis represents chemical shift (δ), and the vertical axis represents relative intensity (ppm).

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

[Photobase generator]
In the present invention, an ionic photobase generator of a carboxylic acid and a base represented by the following general formula (1) is used.

(In the formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, and at least one of X ₁ and X ₂ is an electron-withdrawing group; Is an electron donating group and B is a base, where the substituent is a group other than a hydrogen atom.)

The photobase generator has a structure in which an electron-withdrawing group and an electron-donating group are directly bonded to a meta position and a para position of a benzene ring derived from phenylacetic acid, respectively. A base can be generated depending on such a structure.

In addition, the above structure makes it possible to produce a photobase generator having high sensitivity even at i-line (365 nm). Preferably the molar extinction coefficient at the i-line of the photobase generator is 300L ^· mol ^{-1 · cm} -1 or more, more preferably 500L ^· mol ^{-1 · cm} -1 or _more, 1100L · mol ^- More preferably, it is ¹ · cm ⁻¹ or more. The higher the molar extinction coefficient, the higher the sensitivity. The upper limit of the molar extinction coefficient is not particularly limited, but is, for example, 20000 L · mol ⁻¹ · cm ⁻¹ or less from the viewpoint of light stability and storage stability.

Furthermore, since the photobase generator has a high thermal decomposition temperature (Td), it is excellent in thermal stability when, for example, the coating film is dried. The Td of the photobase generator is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and most preferably 180 ° C. or higher. The thermal decomposition temperature (Td) refers to the temperature at which the weight loss rate becomes 10%.

As the actinic rays for the photobase generator, visible rays, ultraviolet rays, electron beams, X-rays and the like can be irradiated, and ultraviolet rays, particularly 248 nm, 365 nm, 405 nm, and 436 nm are preferably used.

In the general formula (1), R ₁ , R ₂ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent. Examples of the substituent include halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphonyl group. , Phosphono group, phosphonate group, alkoxy group, amide group or organic group.
Here, the organic group is a group containing a carbon atom, for example, a group having 10 or less carbon atoms, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom). (A fluorine atom, a chlorine atom, etc.)).
The electron-withdrawing group that X ₁ and X ₂ can take is not particularly limited, and examples thereof include —C≡N, —COCH ₃ , —NO ₂ , and halogens such as —F, —Cl, —Br, and —I. Atom. Of the electron withdrawing groups, —NO ₂ is preferred. When only _one of X ₁ and X ₂ is an electron withdrawing group, the other is not particularly limited.

The electron-donating group that Y can take is not particularly limited. For example, —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , —C (CH ₃ ) ₃ , —C ₆ H ₅ , — OH, -OCH _3, and include _-OC 6 _{H 5.} Of these, —OCH ₃ is preferable.

Although the substituent which R < ₁ > and R < ₂ > can take is not specifically limited, For example, an electron-donating group is mentioned. R ₁ and R ₂ are each preferably a hydrogen atom.

Substituents that R ₃ and R ₄ can take are not particularly limited. For example, halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, cyano groups, nitro groups, nitroso groups, sulfino groups, sulfo groups , Sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups or organic groups, which may be the same or different. R ₃ and R ₄ are each preferably a hydrogen atom.
Note that R ₁ , R ₂ , X ₁ , X ₂ and Y preferably do not form a cyclic structure.

Although the base which B shows is not specifically limited, For example, primary amines, secondary amines, amines such as tertiary amines (amine compounds), nitrogen-containing cyclic compounds such as pyridine, hydrazine compounds, amide compounds, water An oxide quaternary ammonium salt or the like can be used. In addition, for example, a base such as an amine disclosed in International Publication No. WO2009 / 19979 may be used. Among the bases, secondary amines, tertiary amines, and nitrogen-containing cyclic compounds are preferable. The base represented by B is preferably a strong base.

Examples of the base include 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethyl-4-aminopyridine (DMAP), 1-azabicyclo [2.2, as shown below. .2] Octane (ABCO), 1,8-bis (dimethylamino) naphthalene (DMAN), diazabicycloundecene (DBU), diazabicyclononene (DBN), 1,1,3,3-tetramethylguanidine (TMG), 2-ethyl-4-methylimidazole (2E4MZ), piperidine (PPD), 1-ethyl-piperidine (EPPD), dibutylamine (DBA), 1,5,7-triazabicyclo [4.4. 0] Dec-5-ene (TBD) and the like.

The base preferably has a pKa of 8 to 20, more preferably 10 to 16.

The base is preferably DMAP, DMAN, DBU, TMG, 2E4MZ, PPD, EPPD, DBA and TBD.

The photobase generator is preferably a photobase generator represented by the following general formula (2).

In formula (2), X ₁ , X ₂ , Y and B are the same as in formula (1).

The photobase generator is more preferably a photobase generator represented by the following general formula (3).

In Formula (3), B is the same as Formula (1).

Hereinafter, specific examples of the photobase generator include photobase generators prepared with 4-methoxy-3-nitrophenylacetic acid (MONPA) and various bases, but are not limited thereto.

The photobase generator may be used alone or in combination of two or more. The blending amount of the photobase generator is preferably 3 to 50% by mass, and more preferably 10 to 30% by mass based on the total amount of the photosensitive resin composition.

The photosensitive resin composition of the present invention may contain a photobase generator other than the photobase generator as long as the effects of the present invention are not impaired.

(Polymer precursor)
The photosensitive resin composition of the present invention can contain a polymer precursor as a resin component that is modified using a base generated from the photobase generator as a catalyst. Examples of the polymer precursor include a polymer precursor having a repeating unit of polyamic acid or polyamic acid ester as a polyimide precursor.

The polymer precursor having a repeating unit of polyamic acid or polyamic acid ester is preferably represented by the following general formula (4).

In formula (4), R ₇ is a tetravalent organic group, R ₈ is a divalent organic group, and R ₁₁ is a divalent organic group. Examples of R ₁₁ include a phenol group, an alkylphenol group, a (meth) acrylate group, a cyclic alkyl group, a cyclic alkenyl group, a hydroxyamidic acid group, an aromatic or aliphatic ester group, an amide group, an amideimide group, a carbonate ester group, Examples thereof include a group containing a siloxane group, an alkylene oxide, a urethane group, an epoxy group, an oxetanyl group, or the like as a constituent component. Here, the organic group is a group containing a carbon atom.

M is an integer of 1 or more, and n is 0 or an integer of 1 or more. Here, the preferred number average molecular weight of the polymer precursor is 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.

In the formula (4), R ₇ and R ₈ are aromatic groups, preferably aromatic groups having 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups having 4 to 20 carbon atoms, depending on applications. Selected from the group. R ₇ and R ₈ are preferably the following acid dianhydrides used in the production of the polymer precursor and substituents R ₇ and R ₈ contained in the diamine.

Moreover, when patterning the photosensitive resin composition with short wavelength light, it is preferable to use an aliphatic group as R ₇ and R ₈ from the viewpoint of the absorption characteristics of the polymer. For example, when a group containing fluorine is used as R ₇ and R ₈ , the wavelength of light absorption can be reduced or the dielectric characteristics can be improved.

In the present invention, it is important that the structure of the polymer precursor can be selected according to the application.

Incidentally, tetravalent R ₇ shows only valence for bonding with the acid but, R ₇ may have a substituent. Similarly, the divalent value of R ₈ indicates only the valency for bonding to the amine, but may have other substituents.

R ₉ and R ₁₀ are a hydrogen atom, a monovalent organic group, or a functional group having silicon.

When R ₉ and R ₁₀ are monovalent organic groups, examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. When R ₉ and R ₁₀ are a functional group having monovalent silicon, examples thereof include a siloxane group, a silane group, and a silanol group. In addition, only a part of R ₉ and R ₁₀ can be hydrogen or a monovalent organic group, whereby the solubility can be controlled.

A polyamic acid in which R ₉ and R ₁₀ are hydrogen atoms is preferably used as the polymer precursor. Thereby, alkali developability becomes favorable and a favorable pattern is obtained.

(Polyamic acid)
The polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared simply by mixing acid dianhydride and diamine in a solution. It is preferably used because it can be synthesized by a one-step reaction, can be obtained easily and at low cost, and does not require further modification. The method for synthesizing the polymer precursor is not particularly limited, but a known method can be applied.

Examples of tetracarboxylic dianhydrides that can be used in the present invention include those represented by the following general formula (5). However, the specific examples shown below are merely examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.

(R ₇ in the formula is as described above.)

Incidentally, R ₇ groups in the repeating units in the polyamic acid according to the present embodiment is preferably derived from the R ₇ of the tetracarboxylic dianhydride used as a raw material for polyamic acid production.

Examples of acid dianhydrides applicable to the production of the polymer precursor include 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [ 1,2-c] furan-1,3-dione, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides; pyromellitic dianhydrides, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydrides, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetraca Boronic acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6 '-Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2 , 3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3 3,3-hexafluoro Lopan dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4- Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) Phenoxy] phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-di Carboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-di) Carboxy) phenoxy] biphenyl dianhydride, 4, 4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3 -(1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- ( 1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3 3-hexafluoropro Dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, Pyridinetetracarboxylic dianhydride, sulfo Rudiphthalic anhydride, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, etc. An aromatic tetracarboxylic dianhydride etc. are mentioned.

These may be used alone or in combination of two or more. As a particularly preferred tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan -1,3-dione, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1, Examples include 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 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.

A plurality of carboxyl groups of the acid dianhydride may be present on a single aromatic ring or a plurality of aromatic rings. For example, an acid dianhydride represented by the following formula is used. be able to.

Examples of amines that can be used in the present invention include diamines represented by the following general formula (6). However, the following are examples, and it goes without saying that known ones can be used as long as they do not contradict the gist of the present invention.

(R ₈ in the formula is as described above.)

Examples of diamines when the R ₈ group is a divalent aromatic group include paraphenylenediamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4 ′. -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4 '-Diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biff Nyl, 4,4′-bis (3-aminophenoxybiphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 4-aminophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3 3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, metaphenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether 1,4-bis (4-aminophenoxy) benzene and 1,3-bis (4-aminophenoxy) benzene.

Examples of diamines when the R ₈ group is a divalent aliphatic group include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, Octamethylenediamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine And tricyclo [6.2.1.02,7] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), and isophoronediamine.

Another example is diaminopolysiloxane represented by the following general formula (11).

However, in the formula, R ₂₈ and R ₂₉ each independently represent a divalent hydrocarbon group, and R ₃₀ and R ₃₁ each independently represent a monovalent hydrocarbon group. p is 1 or more, preferably an integer of 1 to 10.

Specifically, R ₂₈ and R ₂₉ in the formula (11) are an alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group or a propylene group, or an arylene group having 6 to 18 carbon atoms such as a phenylene group. Examples of R ₃₀ and R ₃₁ include an alkyl group having 1 to 7 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group.

Also, polyamic acid ester can be suitably used as the polymer precursor. The polyamic acid ester can be obtained by a known method.

For example, an acid anhydride such as 3,3'-benzophenone tetracarboxylic dianhydride and an alcohol such as ethanol are reacted to form a half ester. The half ester is converted to diester diacid chloride using thionyl chloride. An ester of polyamic acid can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.

In the photosensitive resin composition, as a polymer precursor having at least a part of a polyamic acid or a polyamic acid ester repeating unit, a single type of material may be used, or a plurality of types may be used as a mixture. Also good. Further, it may be a copolymer in which at least one of R ₇ and R ₈ has a plurality of structures.

Moreover, you may obtain polyamic acid ester by making half-ester obtained by making said acid anhydride and alcohol react with diisocyanates, such as isophorone diisocyanate. In addition, the synthetic method using diisocyanate can synthesize | combine polyamic acid ester more simply than the synthetic method using said diamine.
Examples of the diisocyanate that can be used for obtaining the polyamic acid ester include diisocyanates represented by the following general formula (7). However, the following are examples, and known ones can be used as long as they do not contradict the gist of the present invention.

(R ₈ in the formula is as described above.)

Examples of the diisocyanate include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), methylene diphenyl 4,4′-diisocyanate (MDI), 2,2-bis (4-isocyanatophenyl) hexafluoropropane, hexa And methylene diisocyanate (HMDI).

The polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).

(In the formula (4-1), as in the general formula (4), R ₇ is a tetravalent organic group, R ₈ is a divalent organic group, and R ₁₁ is a divalent organic group. M is an integer of 1 or more, and n is 0 or an integer of 1 or more, and R _9-1 and R _10-1 may be the same or different from each other, and may be a monovalent organic group or silicon. R ₈ is preferably any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group.)

In formula (4-1), the tetravalent organic group represented by R ₇ is not particularly limited, and may be selected according to the application. For example, an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms. R ₇ is preferably a substituent R ₇ contained in the acid dianhydride represented by the general formula (5) used in the production of the polymer precursor.

In the polyamic acid ester having the structure represented by the general formula (4-1), in particular, from the viewpoint of resolution, R ₇ is a tetravalent containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring. The organic group is preferably a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a tetravalent organic group containing a fluorine atom.

The tetravalent organic group containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthalene group, particularly a phenyl group), and preferably has a trifluoromethyl group and an aromatic group.

The polyamic acid ester having the structure represented by the general formula (4-1) has a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2). It is preferable.

(In the formula (4-1-1), R ₈ , R _9-1 , R _10-1 , R ₁₁ , m and n are the same as in the formula (4-1).)

(In formula (4-1-2), R ₈ , R _9-1 , R _10-1 , R ₁₁ , m and n are the same as in formula (4-1).)

R ₈ in formula (4-1) is preferably any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene group. The phenylene group and the alkylene group are directly bonded to the two nitrogen atoms bonded to R ₈ in the formula (4-1). On the other hand, the alicyclic skeleton and the bisphenylene skeleton bonded by the alkylene group may be directly bonded to the two nitrogen atoms bonded to R ₈ in the formula (4-1) or not. Good. R ₈ is preferably a substituent R ₈ contained in the diamine represented by the general formula (6) or the diisocyanate represented by the general formula (7) used in the production of the polymer precursor.

The group having the alicyclic skeleton in R ₈ may have a substituent and may form a condensed ring. The group having an alicyclic skeleton is preferably represented by the following general formula (8A).

(In the formula (8A), n1 represents an integer of 0 to 10, R _8A1 represents an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, and R _8A2 represents Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.)

The phenylene group for R ₈ may have a substituent and may form a condensed ring. The phenylene group is preferably represented by the following general formula (8B).

(In Formula (8B), n2 represents an integer of 0 to 4, and R _8B1 each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group.)

The group having a bisphenylene skeleton bonded to the alkylene group in R ₈ may have a substituent and may form a condensed ring. The group having a bisphenylene skeleton bonded with the alkylene group is preferably represented by the following general formula (8C).

(In the formula (8C), n3 and n4 each independently represents an integer of 0 to 4, and R _8C1 and R _8C2 are each independently an aliphatic group or an aromatic group, preferably a methyl group, an ethyl group, etc. R _8C3 represents an alkylene group having 1 to 5 carbon atoms.)

The alkylene group represented by R _8C3 in formula (8C) may have a substituent such as an aliphatic group or an aromatic group.

The alkylene group for R ₈ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. Incidentally, the alkylene group in R ₈ may have a substituent such as an aliphatic group or an aromatic group.

R ₈ is preferably a group having an alicyclic skeleton because of excellent resolution, and more preferably a group having an alicyclic skeleton and no aromatic skeleton.

In the present invention, R _9-1 and R _{10-1 in} formula (4-1) are each independently a monovalent organic group or a functional group having silicon. Examples of the monovalent organic group in R _9-1 and R _10-1 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Examples of the functional group having monovalent silicon in R _9-1 and R _10-1 include a siloxane group, a silane group, and a silanol group.

R _9-1 and R _10-1 in the formula (4-1) are preferably alkyl groups from the viewpoint of solubility during the synthesis of the polyamic acid ester. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Here, the alkyl group is preferably a butyl group, a pentyl group, or a hexyl group.

In the present invention, R ₁₁ in the formula (4-1) is a divalent organic group such as an aromatic or aliphatic ester group, an amide group, an amidoimide group, a siloxane group, an epoxy group, or an oxetanyl group. A group included as at least a part of the structure can be given.

Hereinafter, other components that can be blended in the photosensitive resin composition of the present invention will be described.

The solvent that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve a photobase generator, a polymer precursor, and other additives. Examples include N, N′-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Examples include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited. For example, the solvent may be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the polymer precursor depending on the coating film thickness and viscosity.

A sensitizer can also be added to the photosensitive resin composition of the present invention in order to further improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal) cyclohexanone. 2,6-bis (4′-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) Chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p- Dimethylaminophenylvinylene) benzothiazole, 2- (p-di Acetylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4′-dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7 -Diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3- Ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid Amyl, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benz And thiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. 4- (1-Methylethyl)- It is preferable to use thioxanthones such as 9H-thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor.

In addition, an adhesion aid can be blended with the photosensitive resin composition of the present invention in order to improve the adhesion to the substrate. Any known adhesion assistant can be used as long as it is not contrary to the gist of the present invention. For example, γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N- [3- ( And (triethoxysilyl) propyl] phthalamic acid, a reaction product of benzophenonetetracarboxylic dianhydride and (triethoxysilyl) propylamine. The blending amount of the adhesion assistant is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer precursor.

In addition, a base proliferating agent may be added to the photosensitive resin composition of the present invention. When forming a thick film pattern, the decomposition rate of the same amount of photobase generator is required from the surface to the bottom. In this case, in order to improve sensitivity, the addition of a base proliferating agent is preferable. For example, the base proliferating agents disclosed in JP 2012-237776 A, JP 2006-282657 A, and the like can be used.

In addition, you may add to the photosensitive resin composition of this invention the other photosensitive component which generates an acid with light in the range which does not impair the film | membrane characteristic after hardening significantly. When adding a compound having one or more ethylenically unsaturated bonds to the photosensitive resin composition of the present invention, a photo radical generator may be added.

In order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various other 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. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, fibers, and the like.

The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film (support). The dry film is formed by diluting the photosensitive resin composition of the present invention with the above-mentioned organic solvent and adjusting the viscosity to an appropriate viscosity, followed by comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer Apply a uniform thickness on a carrier film with a roll coater, gravure coater, spray coater, etc. Thereafter, the applied photosensitive resin composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 μm.

After the resin layer made of the photosensitive resin composition of the present invention is formed on the carrier film, a peelable cover film is further formed on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to laminate. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.

Next, as an example of a method for producing a patterned film as a cured product using the photosensitive resin composition of the present invention, a case where a polyamic acid ester that is a polyimide precursor is blended as a polymer precursor will be described.

First, as Step 1, a photosensitive resin composition is applied on a substrate and dried to obtain a coating film. As a method for coating the photosensitive resin composition on the substrate, methods conventionally used for coating the photosensitive resin composition, such as spin coater, bar coater, blade coater, curtain coater, screen printer, etc. The method of apply | coating, the method of spray-coating with a spray coater, Furthermore, the inkjet method etc. can be used. As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable that the coating film be dried under conditions such that imidation of the polyamic acid ester in the photosensitive resin composition does not occur. Specifically, natural drying, blast drying, or heat drying can be performed at 20 to 140 ° C. for 1 minute to 1 hour. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 1 minute to 1 hour.

The base material is not particularly limited, and can be widely applied to silicon wafers, wiring boards, various resins, metals, and passivation protective films for semiconductor devices.

Also, since imidization at low temperature is possible, it is characterized by being widely applicable to members and materials that are not suitable for high-temperature processing such as printed wiring board substrates.

Next, in step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light having a wavelength capable of activating the photobase generator to generate a base is used. As described above, the photosensitivity can be adjusted by appropriately using a sensitizer. As the exposure apparatus, a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.

Subsequently, in step 3, heating is performed so as to promote imidization of the coating film by the base generated in the coating film. Thereby, the base generated in the exposed portion in Step 2 serves as a catalyst, and the polyamic acid ester is partially imidized. The heating time and heating temperature are appropriately changed depending on the polyamic acid ester used, the coating film thickness, and the type of photobase generator. Typically, in the case of a coating film thickness of about 10 μm, it is about 2 to 10 minutes at 110 to 200 ° C. If the heating temperature is too low, partial imidization cannot be achieved efficiently. On the other hand, if the heating temperature is too high, imidization of the unexposed area proceeds to reduce the difference in solubility between the exposed area and the unexposed area, which may cause a problem in pattern formation.

Next, in step 4, the coating film is treated with a developer. Thereby, the pattern film which consists of a polyamic acid ester and the partially imidized polyimide can be formed on a base material.

As a method used for the development, an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution of quaternary ammonium salts such as Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant can be used in an appropriate amount as an aqueous solution. Thereafter, the coating film is washed with a rinse liquid as necessary to obtain a pattern film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination.
Examples of the developer include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, hexamethylphosphoryl tri Amide, methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropio Organic solvents such as nate, 2-heptanone, ethyl acetate, diacetone alcohol may be used.

Thereafter, in step 5, the pattern film is heated. The heating temperature is appropriately set so that the polyimide pattern film can be cured. For example, heating is performed in an inert gas at 150 to 300 ° C. for about 5 to 120 minutes. A more preferable range of the heating temperature is 150 to 250 ° C, and a more preferable range is 180 to 220 ° C. The heating is performed by using, for example, a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. At this time, the atmosphere (gas) may be air, or an inert gas such as nitrogen or argon.

The use of the photosensitive resin composition of the present invention is not particularly limited. For example, printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical member, etc. And various known fields and products in which resin materials are used. In particular, a wide range of fields and products in which the properties of polyimide film such as heat resistance, dimensional stability, and insulation are effective, such as paint or printing ink, color filters, flexible display films, semiconductor devices, electronic components, It is suitably used as a material for forming an interlayer insulating film, a wiring coating film such as a solder resist, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member or a building material.

In particular, when a polyimide precursor is contained as a polymer precursor, the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed thereby is a permanent film made of polyimide. Functions as a component that imparts heat resistance and insulation as a film, such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films such as solder resists and coverlay films, solder dams, It is suitable for forming an optical circuit, an optical circuit component, an antireflection film, other optical members or electronic members.

In the present invention, the base generator can be produced by mixing a carboxylic acid represented by the following general formula (8) and a base.

The carboxylic acid is more preferably a carboxylic acid represented by the following general formula (9), further 4-methoxy-3-nitrophenylacetic acid (MONPA) represented by the following formula (10). preferable.

In the formulas (8) and (9), R ₁ to R ₄ , X ₁ , X ₂ and Y are the same as those in the general formula (1).

As the base, a base represented by B in the general formula (1) can be used.

The mixing of the carboxylic acid and the base is preferably carried out by dripping the base solution into the carboxylic acid solution in the dark.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

[Synthesis of carboxylic acid]
(Reference Synthesis Example 1: Synthesis of 4-methoxy-3-nitrophenylacetic acid (MONPA))
In a 500 ml two-necked eggplant flask, 30 ml of concentrated nitric acid (67 mass%) and 3.32 g (20.0 mmol) of 4-methoxyphenylacetic acid (MOPA) were mixed and stirred (room temperature, 6 h). The obtained mixture was added dropwise to cold water, subjected to suction filtration, and then washed with cold water to obtain 4-methoxy-3-nitrophenylacetic acid (MONPA) as a pale yellow solid (yield: 2.51 g). Yield: 60%).

[Synthesis of photobase generator]
Example 1-1 Synthesis of MOMPA-TBD
In a 50 ml eggplant flask, 0.300 g (1.42 mmol) of 4-methoxy-3-nitrophenylacetic acid (MONPA) synthesized above dissolved in 10 ml of dry ethanol and 1,5,7 dissolved in 10 ml of dry ethanol -Triazabicyclo [4.4.0] dec-5-ene (TBD) (0.198 g, 1.42 mmol) was mixed and stirred overnight at room temperature. The resulting mixture was concentrated and reprecipitated with EtOH / Et ₂ O to give MOMPA-TBD as an orange viscous liquid (yield: 0.289 g, yield: 58%). A chart of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 1, and peak analysis results are shown below.

δ1.96 (quint, J = 5.9 Hz, 4H, -CH _2- ), 3.1-3.4 (m, 8H, -NCH _2- ), 3.53 (s, 2H, Bn-H), 3.92 (s, 3H, -OCH ₃ ), 7.00 (d, J = 8.6 Hz, 1H, Ar-H), 7.51 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.85 (d, J = 2.2 Hz, 1H, Ar-H), 10.64 (br, 1.4H, NH).

Example 1-2 Synthesis of MOMPA-DBU
0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 was added to 0.216 g of diazabicycloundecene (DBU) ( MOMPA-DBU was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 except for changing to 1.42 mmol) (yield: 0.419 g, yield: 81%). A chart of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 2, and peak analysis results are shown below.

δ1.6-1.8 (m, 6.7H, -CH _2- ), 1.99 (quint, J = 6.0 Hz, 2H, -CH _2- ), 2.7-2.9 (m, 2H,
-CH _2- ), 3.3-3.5 (m, 6H, -NCH _2- ), 3.56 (s, 2H, Bn-H), 3.92 (s, 3H, -OCH ₃ ), 6.99 (d, J = 8.6 Hz , 1H, Ar-H), 7.53 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.86 (d, J = 2.2 Hz, 1H, Ar-H).

(Example 1-3: Synthesis of MOMPA-2E4MZ)
In Synthesis Example 1, 0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) was added to 2-ethyl-4-methylimidazole (2E4MZ) 0. MOMPA-2E4MZ was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 except that the amount was changed to .156 g (1.42 mmol) (yield: 0.186 g, yield: 41%). A chart of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 3, and peak analysis results are shown below.

δ1.12 (t, J = 7.6 Hz, 6H, -CH ₂ CH ₃ ), 2.15 (s, 3H, -CH ₃ ), 2.65 (q, J = 7.6 Hz, 2H, -CH ₂ CH ₃ ), 3.61 (s, 2H, Bn-H), 3.93 (s, 3H, -OCH ₃ ), 6.56 (s, 1H, Im-H), 7.01 (d, J = 8.6 Hz, 1H, Ar-H), 7.48 ( dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.82 (d, J = 2.2 Hz, 1H, Ar-H).

(Example 1-4: Synthesis of MOMPA-DBA)
0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 and 0.184 g (1.42 mmol) of dibutylamine (DBA) ) MOMPA-DBA was obtained as an orange solid (yield: 0.473 g, yield: 98%) in the same manner as in Synthesis Example 1 except that The chart of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 4, and the peak analysis results are shown below.

δ0.86 (t, J = 7.3 Hz, 6H, -CH ₃ ), 1.26 (sext, J = 7.3 Hz, 4H, -CH _2- ), 1.4-1.6 (m, 4H, -CH _2- ), 2.6 -2.7 (m, 4H, -CH _2- ), 3.47 (s, 2H, Bn-H), 3.93 (s, 3H, -OCH ₃ ), 6.99 (d, J = 8.6 Hz, 1H, Ar-H) , 7.44 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 7.81 (d, J = 2.2 Hz, 1H, Ar-H).

(Comparative Example 1-1: Synthesis of photobase generator described in Japanese Patent No. 4830435)
Ketoprofen (5.09 g, 20 mmol) and 1,4-diazabicyclo [2.2.2] octane (1.12 g, 10 mmol) were placed in a flask and heated at 50 ° C. to completely dissolve ketoprofen and 1,4-diazabicyclo [ 2.2.2] Cyclohexane was slowly added until octane was dissolved. After cooling, a white precipitate was obtained. The photobase generator shown below was obtained by drying under reduced pressure at 45 ° C. for 2 hours.

[Measurement of molar extinction coefficient of photobase generator]
About each photobase generator synthesized above, UV-vis spectrum was measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the molar extinction coefficient at i-line (365 nm) was measured. A solution cell made of quartz and having an optical path length of 1 cm was used. The molar extinction coefficient is a value obtained by dividing the absorbance of the solution by the thickness of the absorbing layer and the molar concentration of the solute. The results are shown in Table 1.

It can be seen that the photobase generators of Examples 1-1 to 1-4 satisfying the general formula (1) have a high molar extinction coefficient at i-line.

[Evaluation of heat resistance of photobase generator]
The photobase generator (MONPA-TBD) of Example 1-1 was measured using a TG-DTA2000S manufactured by Mac Science Co., Ltd. (TG-DTA measurement (temperature increase rate 5 ° C./min)) and stable up to about 200 ° C. I confirmed that there was.

[Synthesis of polyamic acid ester]
(Synthesis Example 1: Synthesis of polyamic acid ester A-1)
About 25 g of dry tert-butyl alcohol was added to 5 g of 6FDA (4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride) as an acid dianhydride and refluxed. An almost transparent liquid was obtained for about 30 minutes after the start of reflux. Further, the mixture was refluxed for about 5 hours, cooled, and filtered through a filter having a pore size of 0.7 μm to remove impurities. By drying under reduced pressure, tert-butyl alcohol was completely removed to obtain acid anhydride half esters as shown in Table 1 as white crystals.
A 100 ml three-necked flask was charged with 5 mmol of the acid anhydride half ester described in Table 1 and 0.0125 mmol of anhydrous 3-methyl-1-phenyl-2-phospholene 1-oxide, and then 10 ml of nitrogen was allowed to flow. Dissolved with dehydrated sulfolane. As the diisocyanate, 5 mmol of anhydrous ITI (isophorone diisocyanate) was dissolved in 5 ml of dehydrated sulfolane and added dropwise to the flask in about 5 minutes. The mixed solution was reacted at 200 ° C. for 3 hours and precipitated with 500 ml of MeOH. The solution including the precipitate was filtered and dried to obtain a polymer precursor polymer. The obtained polymer was dissolved in DMAc (N, N-dimethylacetamide) and reprecipitated with MeOH. Filtration and drying were performed to prepare a 15% by mass polyamic acid ester A-1 solution using dehydrated DMAc as a solvent.

(Synthesis Example 2: Synthesis of polyamic acid ester A-2)
As acid dianhydride, 6FDA is converted to TDA (1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1, A polyamic acid ester A-2 solution was prepared in the same manner as in Synthesis Example 1 except that the compound was changed to 3-dione).

(Synthesis Example 3: Synthesis of polyamic acid ester A-3)
3.75 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.86 g of 4,4′-diaminodiphenyl ether (DDE) were dissolved in 30 g of N-methylpyrrolidone (NMP). The mixture was stirred at 60 ° C. for 4 hours and then at room temperature overnight to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added thereto under water cooling, and the mixture was stirred at room temperature for 3 hours, and 1.73 g of ethanol was added. The reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to prepare a solution of polyamic acid ester A-3. The number average molecular weight of the polyamic acid ester A-3 was 27000.

Example 2-1
Photobase generators are blended and dissolved in the polyamic acid ester solution obtained above at the blending ratio (mass ratio) described in the following table, and the photosensitive resin compositions of Examples and Comparative Examples are used. Got. In addition, the compounding quantity of the polyamic acid ester in a table | surface shows solid content.

The photosensitive resin composition of Example 2-1 in the following table was applied on a 4-inch silicon wafer by spin coating, and heated on a hot plate at 80 ° C. for 20 minutes to form a photosensitive resin composition having a thickness of 10 μm. A material film was formed. The film was exposed with a light amount in the range of 0 to 1000 mJ / cm ² through a mask pattern by a high pressure mercury lamp exposure apparatus equipped with an i-line filter. After the exposure, it was heated on a hot plate at 140 ° C. for 10 minutes, and then immersed in a developer mixed with a tetramethylammonium hydroxide 2.38% aqueous solution and 2-propanol at a weight ratio of 1: 1 for 90 seconds. Pattern development was performed by washing with water for 20 seconds.

As a result, it was confirmed that a pattern was formed by irradiating light with an exposure amount of 150 mJ / cm ² or more.

(Examples 2-2 to 2-9, Comparative Examples 2-1 to 2-3)
In the same procedure as in Example 2-1, a development test was carried out with the blending ratio (mass ratio) and exposure amount shown in the following table, and the exposure amount in which a pattern was formed was confirmed.

* 1: A pattern could not be formed even at 1000 mJ / cm ² .

It can be seen that the photosensitive resin compositions of the examples containing the photobase generator satisfying the general formula (1) are excellent in sensitivity and excellent in pattern formability despite low-temperature curing conditions.

Claims (15)

1. A photosensitive resin composition comprising an ionic photobase generator of a carboxylic acid and a base represented by the following general formula (1).
   

   

   (In the formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, and at least one of X ₁ and X ₂ is an electron-withdrawing group; Is an electron donating group, and B is a base.)
2. The photosensitive resin composition according to claim 1, wherein the photoabsorber has a molar extinction coefficient of 300 L · mol ⁻¹ · cm ⁻¹ or more.
3. In the general formula (1), the electron-withdrawing group is selected from the group consisting of —C≡N, —COCH ₃ , —NO ₂ , —F, —Cl, —Br, and —I. The photosensitive resin composition according to claim 1.
4. In the general formula (1), the electron-donating group is —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , —C (CH ₃ ) ₃ , —C ₆ H ₅ , —OH, — 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is selected from the group consisting of OCH ₃ and —OC ₆ H ₅ .
5. The photosensitive resin composition according to claim 1, further comprising a polymer precursor.
6. 6. The photosensitive resin composition according to claim 5, wherein the polymer precursor is at least one of polyamic acid and polyamic acid ester.
7. 6. The photosensitive resin composition according to claim 5, wherein the polymer precursor is a polyamic acid ester having a structure represented by the following general formula (4-1).
   

   

   (In formula (4-1), R ₇ is a tetravalent organic group, R ₈ is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded by an alkylene group, and an alkylene. R _9-1 and R _10-1 may be the same or different from each other, and may be a monovalent organic group or a functional group having silicon, and R ₁₁ may be a divalent organic group. M is an integer of 1 or more, and n is 0 or an integer of 1 or more.)
8. R ₇ in the general formula (4-1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, or a tetravalent group containing an aromatic group and an alicyclic hydrocarbon group. The photosensitive resin composition according to claim 7, wherein the organic resin group is a tetravalent organic group containing a fluorine atom.
9. 6. The polymer precursor is a polyamic acid ester having a structure represented by at least one of the following general formulas (4-1-1) and (4-1-2): The photosensitive resin composition as described.
   

   

   (In the formula (4-1-1), R ₈ is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R _{9 -1} and R _10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)
   

   

   (In the formula (4-1-2), R ₈ is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton joined by alkylene groups, and is either an alkylene group, R _{9 -1} and R _10-1 may be the same or different from each other, and are a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, and m is an integer of 1 or more. And n is 0 or an integer of 1 or more.)
10. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the film.
11. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 9 or the resin layer of the dry film according to claim 10.
12. A printed wiring board comprising the cured product according to claim 11.
13. A photobase generator characterized by being an ionic type of a carboxylic acid and a base represented by the following general formula (1).
    

    

    (In the formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, and at least one of X ₁ and X ₂ is an electron-withdrawing group; Is an electron donating group, R ₁ to R ₄ each independently represents a hydrogen atom or a substituent, and B represents a base.)
14. In the general formula (1), the electron-withdrawing group is selected from the group consisting of —C≡N, —COCH ₃ , —NO ₂ , —F, —Cl, —Br, and —I. The photobase generator according to claim 13.
15. In the general formula (1), the electron-donating group is —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , —C (CH ₃ ) ₃ , —C ₆ H ₅ , —OH, — The photobase generator according to claim 13 or 14, wherein the photobase generator is selected from the group consisting of OCH ₃ and -OC ₆ H ₅ .

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