CN108700805A - Photosensitive polymer combination, dry film, solidfied material, printed circuit board and Photobase generator - Google Patents

Abstract

Provided: a photosensitive resin composition with excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, a printed circuit board having the cured product, and a photoalkali-generating agent with excellent sensitivity. The photosensitive resin composition, etc., is characterized in that it contains: an ionic photoalkali-generating agent formed by a carboxylic acid and a base as shown in the following general formula (1). (In formula (1), _R1 to _R4 , _X1 and _X2 are each independently a hydrogen atom or a substituent, at least one of _X1 and _X2 is an electron-withdrawing group, Y is an electron-donating group, and B represents a base.)

Description

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

technical field

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

Background technique

The method of chemically modifying the resin by using the photobase generator that generates alkali due to the action of light as a catalyst is applied to the fields of photoresist materials, photocurable materials and the like. For example, a photosensitive resin composition is described in Patent Document 1, which is characterized in that it contains: a photobase generator comprising a salt of a carboxylic acid that undergoes photodecarboxylation and a tertiary amine; and a polyimide precursor and /or polybenzoxazole precursors.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 4830435

Contents of the invention

The problem to be solved by the invention

It is required to improve the sensitivity of a photosensitive resin composition containing a photobase generator. If the sensitivity is improved, reaction conditions such as light irradiation conditions for generating bases and heat treatment conditions for thermal curing with bases can be relaxed, and patterning with good resolution is also expected. In addition, if the sensitivity is improved, the range of selection of the above-mentioned reaction conditions is widened, and in consideration of other components in the photosensitive resin composition, the properties of other materials such as the substrate on which the photosensitive resin composition is applied, such as heat resistance, etc. , it is expected that more suitable reaction conditions can be selected than before. However, in the photobase generator described in Patent Document 1, which includes a salt of a carboxylic acid that undergoes photodecarboxylation and a tertiary amine, sufficient sensitivity cannot be obtained.

Therefore, the object of the present invention is to provide: a photosensitive resin composition excellent in sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or a resin layer of the dry film, a cured product having the Printed circuit boards, photobase generators with excellent sensitivity.

solutions to problems

The inventors of the present invention conducted intensive studies in view of the above, and as a result, found that the above-mentioned problems can be solved by using a compound having a specific structure as a photobase generator, and thus completed the present invention.

That is, the photosensitive resin composition of this invention contains the ionic type photobase generator which the carboxylic acid represented by following General formula (1) and a base form, It is characterized by the above-mentioned.

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

In the photosensitive resin composition of the present invention, it is preferable that the photobase generator has a molar absorption coefficient of 300 L·mol ⁻¹ ·cm ⁻¹ or more.

In the photosensitive resin composition of the present invention, preferably, in the aforementioned general formula (1), the electron-withdrawing group is selected from -C≡N, -NO ₂ , -COCH ₃ , -F, -Cl, -Br and -I composed of groups.

In the photosensitive resin composition of the present invention, preferably, in the aforementioned general formula (1), the electron donating group is selected from -CH ₃ , -C ₂ H ₅ , -CH(CH ₃ ) ₂ , -C(CH ₃ ) ₃ , a 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, it is preferable that the aforementioned polymer precursor is at least any one of polyamic acid and polyamic acid ester.

In the photosensitive resin composition of the present invention, it is preferable that the aforementioned 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 with an alicyclic skeleton, a phenylene group, a group with a diphenylene skeleton bonded with an alkylene group Any one of the group and the alkylene group, R _9-1 and R _10-1 are optionally the same or different from each other, a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more.)

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

In the photosensitive resin composition of the present invention, it is preferable that the aforementioned polymer precursor is a polymer having a structure shown in at least any one of the following general formulas (4-1-1) and (4-1-2). Amic acid esters.

( _In the formula (4-1-1), R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group. Or, R _9-1 and R _10-1 are optionally the same or different from each other, and are a monovalent organic group or a functional group with silicon, R ₁₁ is a divalent organic group, m is an integer of 1 or more, and n is An integer of 0 or 1 or more.)

( _In the formula (4-1-2), R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group. Or, R _9-1 and R _10-1 are optionally the same or different from each other, and are a monovalent organic group or a functional group with silicon, R ₁₁ is a divalent organic group, m is an integer of 1 or more, and n is An integer of 0 or 1 or more.)

The dry film of the present invention has 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 aforementioned photosensitive resin composition or the resin layer of the aforementioned dry film.

The printed wiring board of this invention is characterized by having the said hardened|cured material.

The photobase generator of the present invention is characterized in that it is an ion type formed of a carboxylic acid represented by the following general formula (1) and a base.

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

Preferably, in the photobase generator of the present invention, in the aforementioned general formula (1), the electron-withdrawing groups are -C≡N, -COCH ₃ , -NO ₂ , -F, -Cl, -Br and -I.

In the photobase generator of the present invention, preferably, in the aforementioned general formula (1), the electron-donating groups are -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 .

The effect of the invention

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

Description of drawings

FIG. 1 is a graph 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).

Fig. 2 is a graph showing the spectrum of ¹ H-NMR 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).

Fig. 3 is a graph showing the spectrum of ¹ H-NMR 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).

Fig. 4 is a graph showing the spectrum of ¹ H-NMR 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).

Detailed ways

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 formed of a carboxylic acid represented by the following general formula (1) and a base is used.

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

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

Moreover, with the said structure, the photobase generator with high sensitivity also in i-ray (365 nm) can be manufactured. The molar absorptivity coefficient of the aforementioned photobase generator under the i-ray is preferably more than 300L·mol ^-1 ·cm ^-1 , more preferably more than 500L·mol ^-1 ·cm ^-1 , more preferably 1100L·mol ^-1 ·cm ^-1 or more. The higher the molar absorptivity, the higher the sensitivity tends to be. The upper limit of the molar absorptivity is not particularly limited, but is, for example, 20000 L·mol ⁻¹ ·cm ⁻¹ or less from the viewpoint of photostability and storage stability.

Furthermore, since the thermal decomposition temperature (Td) of the said photobase generator is high, it is excellent also in the heat stability at the time of drying of a coating film, for example. Td of the aforementioned photobase generator is preferably 120°C or higher, more preferably 150°C or higher, and most preferably 180°C or higher. In addition, pyrolysis temperature (Td) means the temperature at which the weight loss ratio becomes 10%.

Visible rays, ultraviolet rays, electron beams, X-rays, etc. can be irradiated as active rays for the above-mentioned photobase generator, and ultraviolet rays, especially ultraviolet rays of 248nm, 365nm, 405nm, and 436nm are preferred.

In the aforementioned general formula (1), R ₁ , R ₂ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent. Examples of substituents include halogen atoms, hydroxyl groups, mercapto groups, thio groups, silyl groups, silanol groups, cyano groups, nitro groups, nitroso groups, sulfinyl groups, sulfo groups, sulfonate groups, phosphino groups, Phosphinyl group, phosphoric acid group, phosphono group, phosphonate group, alkoxy group, amide group or organic group.

Here, an organic group refers to a group containing carbon atoms, for example, a group having 10 or less carbon atoms, which may have atoms other than carbon atoms (such as hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc.) Atoms (fluorine atoms, chlorine atoms, etc.) etc.).

The electron-withdrawing groups that can be used for X ₁ and X ₂ are not particularly limited, and examples thereof include -C≡N, -COCH ₃ , -NO ₂ , and halogen atoms such as -F, -Cl, -Br, and -I. Among the electron-withdrawing groups, -NO ₂ is preferred. In addition, when only _one of X1 and X2 is an electron _- withdrawing group, the other is not specifically limited.

The electron-donating group that Y can adopt is not particularly limited, and examples include -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 . Among them, -OCH ₃ is preferred.

_The substituents that R1 and _R2 can adopt are not particularly limited, and examples thereof include electron donating groups. R ₁ and R ₂ are preferably each a hydrogen atom.

_The substituents that _R3 and R4 can adopt are not particularly limited, such as halogen atoms, hydroxyl groups, mercapto groups, thiol groups, silyl groups, silanol groups, cyano groups, nitro groups, nitroso groups, sulfinyl groups, and sulfo groups , sulfonate group, phosphine group, phosphinyl group, phosphono group, phosphonate group or organic group, which may be the same or different. R ₃ and R ₄ are preferably each a hydrogen atom.

It should be noted that R ₁ , R ₂ , X ₁ , X ₂ and Y preferably do not form a ring structure.

The base represented by B is not particularly limited, and for example, amines (amine compounds) such as primary amines, secondary amines, and tertiary amines, nitrogen-containing cyclic compounds such as pyridine, hydrazine compounds, amide compounds, quaternary ammonium hydroxides, and the like can be used. In addition, for example, bases such as amines disclosed in International Publication No. WO2009/19979 can 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[2.2.2]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]-5-decene (TBD), etc.

The pKa of the aforementioned base is preferably 8-20, more preferably 10-16.

The aforementioned bases are preferably DMAP, DMAN, DBU, TMG, 2E4MZ, PPD, EPPD, DBA and TBD.

The aforementioned 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).

In addition, the above-mentioned 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, as specific examples of the aforementioned photobase generator, photobase generators prepared using 4-methoxy-3-nitrophenylacetic acid (MONPA) and various bases are shown, but are not limited thereto.

The said photobase generator may be used individually by 1 type, and may use it in combination of 2 or more types. As for the compounding quantity of the said photobase generator, 3-50 mass % is preferable based on the photosensitive resin composition whole quantity, More preferably, it is 10-30 mass %.

The photosensitive resin composition of this invention can contain photobase generators other than the said photobase generator in the range which does not impair the effect of this invention.

(polymer precursor)

In the photosensitive resin composition of the present invention, a polymer precursor may be contained as a resin component modified using the base generated from the photobase generator as a catalyst. As a polymer precursor, the polymer precursor which has the repeating unit of a polyamic acid or a polyamic acid ester is mentioned, for example as a polyimide precursor.

The polymer precursor having the repeating unit of the aforementioned 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: phenol group, alkylphenol group, (meth)acrylate group, cyclic alkyl group, cyclic alkenyl group, hydroxyamic acid group, aromatic or aliphatic ester group, amide group, amidoimide group, carbonate group, siloxane group, alkylene oxide group, urethane group, epoxy group, oxetanyl group, etc. as constituent groups. Here, an organic group refers to a group containing carbon atoms.

m is an integer of 1 or more, and n is an integer of 0 or 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 still more preferably 10,000 to 200,000.

In formula (4), R ₇ and R ₈ are selected from aromatic groups, preferably aromatic groups with 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups with 4 to 20 carbon atoms according to the application group. R ₇ and R ₈ are preferably substituents R ₇ and R ₈ contained in acid dianhydrides and diamines described later used in the production of the polymer precursor.

Moreover, when patterning a photosensitive resin composition with short-wavelength light, it is preferable to use an aliphatic group as _R7 and _R8 from a viewpoint of the absorption characteristic of a polymer. In addition, for example, when a fluorine-containing group is used as R ₇ and R ₈ , the wavelength reduction of light absorption and dielectric properties can be improved.

In the present invention, it is important to select the structure of the polymer precursor according to the application.

It should be noted that the 4 valency of R ₇ represents only the valence for bonding with an acid, and R ₇ may have a substituent. Similarly, the divalence of R ₈ represents a valence only for bonding with an amine, and may further have a substituent.

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

When R ₉ and R ₁₀ are monovalent organic groups, examples thereof include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. When R ₉ and R ₁₀ are monovalent silicon-containing functional groups, examples thereof include siloxane groups, silane groups, and silanol groups. Furthermore, only a part of R ₉ and R ₁₀ may be hydrogen or a monovalent organic group, thereby controlling the solubility.

As a polymer precursor, polyamic acid in which R ₉ and R ₁₀ are hydrogen atoms is suitably used. Thereby, alkali developability becomes favorable and a favorable pattern can be obtained.

(polyamic acid)

The polyamic acid can be produced by applying a conventionally known method. For example, it can be produced only by mixing an acid dianhydride and a diamine in a solution. It can be synthesized by a one-step reaction, can be obtained easily and at low cost, and does not require further modification, so it is preferably used. The synthesis method of the polymer precursor is not particularly limited, and known methods can be applied.

As an example of the tetracarboxylic dianhydride which can be used in this invention, the tetracarboxylic dianhydride represented by following general formula (5) is mentioned. However, the specific example shown below is an example, and a well-known thing can be used, of course, as long as it does not deviate from the summary of this invention.

(R in the _formula is as shown above.)

In addition, it is preferable that the _R7 group in the repeating unit in the polyamic acid of this embodiment originates in _R7 of the tetracarboxylic dianhydride used as a raw material for polyamic-acid manufacture.

Examples of acid dianhydrides that can be used to produce the above-mentioned polymer precursors include: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3- Furyl)naphtho[1,2-c]furan-1,3-dione, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride Aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4 '-Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2' ,6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane di anhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane di anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1, 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis[(3,4-dicarboxy)benzoyl]phthalic anhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]phthalic anhydride, 2,2-bis{ 4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl} Propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]benzene Base} ketone dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3-(1,2-dicarboxy)benzene Oxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)benzene Oxy]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-Hexafluoropropane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4 -two Carboxyphenyl) propane dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride Dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, pyridine tetracarboxylic dianhydride Carboxylic dianhydride, sulfonyl diphthalic anhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'- Aromatic tetracarboxylic dianhydrides, such as tetracarboxylic dianhydride, etc.

These can be used individually or in mixture of 2 or more types. Furthermore, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furyl)naphthalene can be mentioned as a particularly preferably used tetracarboxylic dianhydride. And[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)-1,1,1,3,3,3-hexafluoropropane dianhydride.

When a fluorine-introduced acid dianhydride or an acid dianhydride having an alicyclic skeleton is used as an acid dianhydride used in combination, physical properties such as solubility and thermal expansion coefficient can be adjusted without greatly impairing transparency. In addition, when rigid acid dianhydrides such as pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride are used, the final The linear thermal expansion coefficient of the polyimide becomes small, but it tends to hinder the improvement of transparency, so it can be used in combination while paying attention to the copolymerization ratio.

A plurality of carboxyl groups of an acid dianhydride may exist on a single aromatic ring or may exist on a plurality of aromatic rings, for example, an acid dianhydride represented by the following formula can be used.

Amines that can be used in the present invention include diamines represented by the following general formula (6). However, the following is an example, and it is of course possible to use known diamines as long as they do not deviate from the spirit of the present invention.

H ₂ NR ₈ -NH ₂ (6)

(R in the _formula is as shown above.)

Examples of _diamines when the R group is a divalent aromatic group include p-phenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-Dimethyl-4,4'-diaminobiphenyl,3,3'-dimethoxy-4,4'-diaminobiphenyl,3,3'-dichloro-4,4'-diamino Biphenyl, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylsulfoxide, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[ 4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 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, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 3,4'- Diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene.

Examples of _diamines when the R group is a divalent aliphatic group include 1,1-m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylene base diamine, hexamethylene diamine, hepta methylene diamine, octamethylene diamine, nonamethylene diamine, 4,4-diamino hepta methylene diamine, 1,4-di Aminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylindanylidene dimethylenediamine, tricyclo[6.2.1.02, 7]-Undecenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), isophoronediamine.

Moreover, as another example, the diamino polysiloxane etc. which are represented by following General formula (11) are mentioned.

Wherein, 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 1-10.

Specifically, examples of R ₂₈ and R ₂₉ in the above formula (11) include alkylene groups having 1 to 7 carbons such as methylene, ethylene, and propylene, and alkylenes having 6 carbons such as phenylene. An arylene group of ∼18, etc., examples of R ₃₀ and R ₃₁ include an alkyl group having 1 to 7 carbons such as a methyl group and an ethyl group, an aryl group having 6 to 12 carbons such as a phenyl group, and the like.

Moreover, polyamic acid ester can also be used suitably as a polymer precursor. Polyamic acid ester can be obtained by a well-known method.

For example, an acid anhydride such as 3,3'-benzophenone tetracarboxylic dianhydride is reacted with an alcohol such as ethanol to form a half ester. The half-ester is formed using thionyl chloride to form the diester diacid chloride. The ester of polyamic acid is obtained by making this diester diacid chloride react with diamines, such as 3, 5- diaminobenzoic acid.

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

Moreover, polyamic acid ester can be obtained by reacting the said acid anhydride and the half ester obtained by reacting alcohol with diisocyanate, such as isophorone diisocyanate. In addition, compared with the synthesis method using the said diamine, the synthesis method using a diisocyanate can synthesize|combine polyamic acid ester simply.

The diisocyanate represented by following general formula (7) is mentioned as diisocyanate which can be used for obtaining polyamic acid ester. However, the following is an example, and a known diisocyanate can be used as long as it does not deviate from the spirit of the present invention.

OCN-R ₈ -NCO (7)

(R in the _formula is as shown above.)

Examples of the aforementioned diisocyanate include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), 4,4'-methylenediphenyl diisocyanate (MDI), 2,2-bis( 4-isocyanatophenyl)hexafluoropropane, hexamethylene diisocyanate (HMDI) and the like.

It is preferable that the said polymer precursor is the polyamic acid ester which has the structure shown by following general formula (4-1).

(In formula (4-1), like aforementioned general formula (4), R ₇ is a 4-valent organic group, R ₈ is a 2-valent organic group, R ₁₁ is a 2-valent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more. R _9-1 and R _10-1 are optionally the same or different from each other, and are monovalent organic groups or functional groups with silicon. R ₈ is preferably a Any of a cyclic skeleton group, a phenylene group, a group having a diphenylene skeleton bonded with 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. Examples thereof include aromatic groups, preferably aromatic groups having 6 to 32 carbon atoms, or aliphatic groups, preferably aliphatic groups having 4 to 20 carbon atoms. R ₇ is preferably a substituent R ₇ contained in the acid dianhydride represented by the aforementioned general formula (5) used in the production of the aforementioned polymer precursor.

For the polyamic acid ester having the structure shown in aforementioned general formula (4-1), from the point of view of resolution, R Especially preferably is the _quaternary organic compound that comprises the condensed ring of aromatic ring and aliphatic hydrocarbon ring group, a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a tetravalent organic group containing a fluorine atom.

The aforementioned tetravalent organic group containing fluorine atoms preferably has an aromatic group (preferably phenyl, naphthyl, especially phenyl), and preferably has a trifluoromethyl group and an aromatic group.

It is preferable that the polyamic acid ester which has the structure shown by said general formula (4-1) has the structure shown by any one of following general formula (4-1-1) and (4-1-2).

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

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

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

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

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

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

The aforementioned group having a diphenylene skeleton bonded with an alkylene group in R ₈ may have a substituent, or may form a condensed ring. The aforementioned group having a diphenylene skeleton bonded with an alkylene group is preferably represented by the following general formula (8C).

(In formula (8C), n3 and n4 independently represent the integer of 0～4 respectively, R _8C1 and R _8C2 are respectively independently aliphatic group or aromatic group, preferably represent the aliphatic group such as methyl, ethyl group, R _8C3 represents an alkylene group with 1 to 5 carbons.)

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

The aforementioned alkylene group in R ₈ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. It should be noted that the aforementioned alkylene group in R ₈ may have a substituent such as an aliphatic group or an aromatic group.

For excellent resolution, R ₈ is preferably a group having an alicyclic skeleton, more preferably a group having an alicyclic skeleton and not having an 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 aforementioned monovalent organic group in R _9-1 and R _10-1 include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like. Examples of the monovalent silicon-containing functional group in R _9-1 and R _10-1 include siloxane groups, silane groups, silanol groups, and the like.

R _9-1 and R _10-1 in formula (4-1) are preferably alkyl groups from the viewpoint of solubility at the time of synthesis of polyamic acid ester. As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned, for example. Alkyl here is preferably butyl, pentyl or hexyl.

In the present invention, R ₁₁ in formula (4-1) is a divalent organic group, for example, include aromatic or aliphatic ester group, amide group, amidoimide group, siloxane group, ring An oxy group, an oxetanyl group, etc. constitute at least a part of the group.

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

The solvent usable 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, diglyme , cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazoline, N-cyclohexyl-2-pyrrolidone, di Methyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. These may be used individually or in mixture of 2 or more types. The amount of the solvent to be used is not particularly limited, and may be used in a range of 50 to 9000 parts by mass relative to 100 parts by mass of the polymer precursor depending on the coating film thickness and viscosity, for example.

In order to further improve photosensitivity, you may add a sensitizer to the photosensitive resin composition of this invention. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane , 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-dimethylaminobenzylidene)-4-methylcyclohexanone, 2, 6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethyl Amino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-Dimethylaminophenylvinylidene)benzothiazole, 2-(p-Dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylamino Benzylidene) acetone, 1,3-bis(4'-diethylaminobenzylidene)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, N-p Tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1- Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2 -(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. From the viewpoint of sensitivity, it is preferable to use 4-(1 Thioxanthones such as -methylethyl)-9H-thioxanth-9-one. These can be used individually or in combination of 2-5 types. It is preferable to use 0.1-10 mass parts of sensitizers with respect to 100 mass parts of polymer precursors.

Moreover, in order to improve the adhesiveness with a base material, the photosensitive resin composition of this invention can also mix|blend an adhesion auxiliary agent. As an adhesion auxiliary agent, well-known adhesion auxiliary agents can be used as long as it does not deviate from the summary of this invention. Examples include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Methoxysilane, γ-mercaptopropylmethyldimethoxysilane, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone tetracarboxylic acid di The reaction product of anhydride and (triethoxysilyl) propylamine, etc. It is preferable that the compounding quantity of an adhesion auxiliary agent exists in the range of 0.5-10 mass parts with respect to 100 mass parts of polymer precursors.

Moreover, you may add a base multiplying agent to the photosensitive resin composition of this invention. When forming a pattern of a thick film, the same degree of decomposition rate of the photobase generator is required from the surface to the bottom. In this case, in order to improve the sensitivity, it is preferable to add a base multiplying agent. For example, base multiplying agents disclosed in JP-A-2012-237776, JP-A-2006-282657, etc. can be used.

In addition, other photosensitive components which generate acid by light can be added to the photosensitive resin composition of this invention within the range which does not significantly impair the film characteristic after hardening. When adding a compound having one or more ethylenically unsaturated bonds to the photosensitive resin composition of the present invention, a photoradical generator may be added.

In addition, various organic or inorganic low-molecular or high-molecular compounds may be compounded in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention. For example, dyes, surfactants, leveling agents, plasticizers, microparticles, etc. can be used. The microparticles include organic microparticles such as polystyrene and polytetrafluoroethylene, inorganic microparticles such as colloidal silica, carbon, and layered silicate, and they may have a porous or hollow structure. Specific materials for obtaining a porous shape and a hollow structure include various pigments, fillers, fibers, and the like.

The dry film of the present invention has a resin layer obtained by coating and drying the photosensitive resin composition of the present invention on a carrier film (support). The formation of the dry film is as follows: the photosensitive resin composition of the present invention is diluted with the above-mentioned organic solvent, adjusted to an appropriate viscosity, and then coated with a comma coater, knife coater, lip coater, rod coater, Die coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. to coat the carrier film with a uniform thickness. 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 is generally suitably selected within the range of 10 to 150 μm, preferably 20 to 60 μm, in terms of the film thickness after drying.

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

After forming a resin layer containing the photosensitive resin composition of the present invention on a carrier film, it is further preferable to laminate a peelable protective film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. As a peelable protective film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used, for example. When peeling a protective film as a protective film, what is necessary is just to be less than the adhesive force of a resin layer and a carrier film.

Next, the case where polyamic acid ester which is a polyimide precursor is compounded as a polymer precursor is demonstrated as an example about the manufacturing method of the pattern film which is a hardened|cured material which used the photosensitive resin composition of this invention.

First, as step 1, a photosensitive resin composition is applied on a substrate and dried to obtain a coating film. As the method of coating the photosensitive resin composition on the base material, the method used in the coating of the conventional photosensitive resin composition can be used, for example, a spin coater, a bar coater, a knife coater, a curtain coater, etc. A method of coating with a cloth machine, a screen printing machine, etc.; a method of spray coating with a spray coater; and an inkjet method, etc. As a drying method of the coating film, methods such as air drying, heat drying in an oven or a hot plate, and vacuum drying are used. Moreover, it is desirable to perform drying of a coating film on the condition which does not cause imidization of the polyamic acid ester in a photosensitive resin composition. Specifically, natural drying, air drying, or heat drying can be performed at 20 to 140° C. for 1 minute to 1 hour. Drying is preferably performed on a hot plate for 1 to 20 minutes. In addition, vacuum drying may also be performed, and in this case, it may be performed at room temperature for 1 minute to 1 hour.

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

In addition, since imidization can be performed at low temperature, it is characterized in that it can be widely used for members and materials that are not suitable for high-temperature treatment, such as substrates of printed circuit boards.

Next, as step 2, the said coating film is exposed through the photomask which has a pattern, or it exposes directly. As the exposure light, light having a wavelength capable of activating the photobase generator to generate a base is used. As mentioned above, when a sensitizer is used appropriately, photosensitivity can be adjusted. As the exposure apparatus, a contact aligner, mirror projection, stepper exposure apparatus, laser direct tracing exposure apparatus, or the like can be used.

Next, as Step 3, heating is performed so that the imidization of the coating film is accelerated by the alkali generated in the coating film. Thereby, the base which arose in the exposure part in the said process 2 becomes a catalyst, and a polyamic acid ester is partially imidized. Heating time and heating temperature are suitably changed according to the polyamic acid ester used, coating film thickness, and the kind 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. When the heating temperature is too low, partial imidation cannot be effectively achieved. On the other hand, if the heating temperature is too high, the imidization of the unexposed area will proceed, and the difference in solubility between the exposed area and the unexposed area will be reduced, which may hinder pattern formation.

Next, as step 4, the coating film is treated with a developing solution. Thereby, the pattern film containing polyamic acid ester and partially imidized polyimide can be formed on a base material.

As the method used for development, any method can be selected from conventionally known photoresist development methods, such as spin spray method, paddle method, dipping method with ultrasonic treatment, and the like. Examples of developing solutions include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, tetramethylammonium hydroxide, and the like. Aqueous solutions of quaternary ammonium salts such as butyl ammonium hydroxide, etc. In addition, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, and isopropanol, or a surfactant can be added to form an aqueous solution and used. Thereafter, if necessary, the coating film is washed with a rinse solution to obtain a patterned film. As rinsing fluids, distilled water, methanol, ethanol, isopropanol, etc. can be used alone or in combination.

In addition, as a developer, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Sulfoxide, γ-butyrolactone, hexamethylphosphoric triamide, methanol, ethanol, isopropanol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate , propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, diacetone alcohol and other organic solvents.

Then, as step 5, the patterned film is heated. The heating temperature is suitably set so that the pattern film of polyimide can be hardened. For example, heating is performed at 150 to 300° C. for about 5 to 120 minutes in an inert gas. The more preferable range of heating temperature is 150-250 degreeC, and the more preferable range is 180-220 degreeC. Heating is performed by using, for example, a hot plate, an oven, or a temperature-raising oven capable of setting a temperature program. As the atmosphere (gas) at this time, air may be used, and an inert gas such as nitrogen or argon may be used.

Applications of the photosensitive resin composition of the present invention are not particularly limited, and examples include printing inks, adhesives, fillers, electronic materials, optical circuit components, molding materials, resist materials, building materials, three-dimensional modeling, optical Various known fields and products using resin materials for members and the like. In particular, it is suitable for a wide range of fields/products where polyimide film properties such as heat resistance, dimensional stability, and insulation are considered to be effective, such as paints or printing inks, or color filters, films for flexible displays, and semiconductors. Forming materials for component devices, electronic components, interlayer insulating films, solder resists, and other wiring cover films, optical circuits, optical circuit components, antireflection films, holograms, optical members, and building materials.

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 patterned film formed thereby serves as a The permanent film of amine functions as a component that imparts heat resistance and insulation. For example, it is suitable for forming wiring such as color filters, films for flexible displays, electronic components, semiconductor devices, interlayer insulating films, solder resist films, and cover films. Cover film, tin bank, optical circuit, optical circuit part, anti-reflection 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) with a base.

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

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

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

The above-mentioned mixing of the carboxylic acid and the base is preferably performed by adding a solution of the base dropwise to a solution of the carboxylic acid in the absence of light.

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to a following Example. It should be noted that the "parts" and "%" in the following are all based on mass unless otherwise specified.

[Synthesis of carboxylic acid]

(Refer to Synthesis Example 1: Synthesis of 4-methoxy-3-nitrophenylacetic acid (MONPA))

In a 500ml two-necked eggplant-shaped bottle, 30ml of concentrated nitric acid (67% by mass) and 3.32g (20.0mmol) of 4-methoxyphenylacetic acid (MOPA) were mixed at 0°C, and stirred (room temperature, 6h). The resulting mixture was added dropwise in cold water, and after suction filtration, washed with cold water to obtain 4-methoxy-3-nitrophenylacetic acid (MONPA) as a pale yellow solid (output: 2.51 g, yield: 60 %).

[Synthesis of Photobase Generator]

(Example 1-1: Synthesis of MOMPA-TBD)

In a 50ml eggplant-shaped bottle, dissolve 0.300g (1.42mmol) of 4-methoxy-3-nitrophenylacetic acid (MONPA) synthesized above in 10ml of dry ethanol, and 1 , 5,7-Triazabicyclo[4.4.0]-5-decene (TBD) 0.198g (1.42mmol) was mixed and stirred overnight at room temperature. The resulting mixture was concentrated and reprecipitated with EtOH/ _Et2O to obtain MOMPA-TBD as an orange viscous liquid (yield: 0.289 g, yield: 58%). The chart of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 1 , and the analysis results of the peaks are shown below.

δ1.96(quint, J=5.9Hz, 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=8.6Hz,1H,Ar-H),7.51(dd,J=8.6,2.2Hz,1H,Ar-H),7.85(d,J=2.2Hz,1H, Ar-H),10.64(br,1.4H,NH).

(Example 1-2: Synthesis of MOMPA-DBU)

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

δ1.6-1.8 (m, 6.7H, -CH ₂ -), 1.99 (quint, J=6.0Hz, 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＝8.6Hz,1H,Ar-H), 7.53(dd, J=8.6, 2.2Hz, 1H, Ar-H), 7.86(d, J=2.2Hz, 1H, Ar-H).

(Example 1-3: Synthesis of MOMPA-2E4MZ)

Change 0.198g (1.42mmol) of 1,5,7-triazabicyclo[4.4.0]-5-decene (TBD) in Synthesis Example 1 to 2-ethyl-4-methylimidazole (2E4MZ) Except for 0.156 g (1.42 mmol), MOMPA-2E4MZ was obtained as an orange viscous liquid in the same manner as in Synthesis Example 1 (amount: 0.186 g, yield: 41%). The chart of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 3 , and the analysis results of the peaks are shown below.

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

(Example 1-4: Synthesis of MOMPA-DBA)

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

δ0.86(t, J=7.3Hz, 6H, -CH ₃ ), 1.26(sext, J=7.3Hz, 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＝8.6Hz,1H,Ar-H) ,7.44(dd,J=8.6,2.2Hz,1H,Ar-H),7.81(d,J=2.2Hz,1H,Ar-H).

(Comparative Example 1-1: Synthesis of photobase generator described in Japanese Patent No. 4830435)

Ketoprofen 5.09g (20mmol) and 1,4-diazabicyclo [2.2.2] octane 1.12g (10mmol) were dropped into the flask, heated at 50°C, slowly dropped into cyclohexane until ketoprofen and 1 ,4-diazabicyclo[2.2.2]octane was completely dissolved. Afterwards, upon cooling, a white precipitate was obtained. It dried under reduced pressure at 45 degreeC for 2 hours, and obtained the photobase generator shown below.

[Determination of Molar Absorption Coefficient of Photobase Generator]

For each photobase generator synthesized above, the UV-vis spectrum was measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the molar absorptivity at i-ray (365 nm) was measured. A cuvette made of quartz and having an optical path length of 1 cm was used as a cuvette for the solution. The molar absorptivity 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.

[Table 1]

It turns out that the photobase generators of Examples 1-1 to 1-4 satisfying the aforementioned general formula (1) have high molar absorptivity coefficients under i-rays.

[Evaluation of heat resistance of photobase generator]

About the photobase generator (MONPA-TBD) of Example 1-1, TG-DTA measurement was performed using TG-DTA2000S manufactured by Mac Science (5 degreeC/min of heating rate), and it confirmed that it was stable up to 200 degreeC vicinity.

[Synthesis of polyamic acid ester]

(synthesis example 1: synthesis of polyamic acid ester A-1)

About 25 g of dry tert-butanol was added to 5 g of 6FDA (4,4'-(hexafluoroisopropylidene) diphthalic anhydride) as an acid dianhydride, and the mixture was refluxed. A substantially clear liquid was obtained about 30 minutes after the initiation of reflux. Further, it was refluxed for about 5 hours, cooled, and filtered through a filter with a pore size of 0.7 μm to remove impurities. After drying under reduced pressure, tert-butanol was completely removed to obtain half esters of acid anhydrides listed in Table 1 as white crystals.

After dropping into a three-necked flask with a capacity of 100 ml, 5 mmol of the half ester of the acid anhydride recorded in Table 1 and 0.0125 mmol of anhydrous 3-methyl-1-phenyl-2-phosphole 1-oxide, nitrogen gas was flowed in, While dissolving with 10ml of dehydrated sulfolane. 5 mmol of anhydrous ITI (isophorone diisocyanate) which is a diisocyanate was dissolved in 5 ml of dehydrated sulfolane, and it was added dropwise to the flask over about 5 minutes. The mixed solution was reacted at 200° C. for 3 hours, and precipitated with 500 ml of MeOH. The solution containing the precipitate was filtered and dried to obtain a high molecular precursor polymer. The resulting polymer was dissolved in DMAc (N,N-dimethylacetamide), and reprecipitated with MeOH. Filtration and drying were performed, and the polyamic acid ester A-1 solution of 15 mass % was produced using dehydrated DMAc as a solvent.

[Table 2]

(synthesis example 2: synthesis of polyamic acid ester A-2)

As the acid dianhydride, 6FDA was changed to TDA(1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furyl)naphtho[1,2 -c] except that furan-1,3-dione), it carried out similarly to the synthesis example 1, and produced the polyamic acid ester A-2 solution.

[table 3]

(Synthesis example 3: synthesis of polyamic acid ester A-3)

7.75 g of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.86 g of 4,4'-diaminodiphenyl ether (DDE) were dissolved in N-methylpyrrolidone ( NMP) 30 g, stirred at 60° C. for 4 hours, then stirred overnight at room temperature to obtain a polyamic acid. To this, under water cooling, 9.45 g of trifluoroacetic anhydride was added, stirred at room temperature for 3 hours, and 1.73 g of ethanol was added. This reaction liquid was dripped in distilled water, the deposit was collected by filtration, and it dried under reduced pressure, and produced the solution of polyamic acid ester A-3. The number average molecular weight of polyamic acid ester A-3 was 27000.

(Example 2-1)

With the compounding ratio (mass ratio) described in the following table, the photobase generator was compounded and dissolved with respect to the solution of the polyamic acid ester obtained above, and the photosensitive resin composition of the Example and the comparative example was obtained. In addition, the compounding quantity of the polyamic acid ester in a table shows solid content quantity.

Apply the photosensitive resin composition of Example 2-1 in the following table on a 4-inch silicon wafer by spin coating, and heat it on a hot plate at 80°C for 20 minutes to form a photosensitive resin composition with a thickness of 10 μm membrane. This film was exposed with a light amount in the range of 0 to 1000 mJ/cm ² through a mask pattern using a high-pressure mercury lamp exposure apparatus equipped with an i-ray filter. After exposure, heat on a hot plate at 140°C for 10 minutes, then immerse in a developer mixed with a 2.38% aqueous solution of tetramethylammonium hydroxide and 2-propanol at a weight ratio of 1:1 for 90 seconds, and then wash with water for 20 seconds , thereby performing pattern development.

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

(Examples 2-2 to 2-9, Comparative Examples 2-1 to 2-3)

By the procedure similar to Example 2-1, the image development test was implemented with the compounding ratio (mass ratio) and exposure amount described in the following table, and the exposure amount of pattern formation was confirmed.

[Table 4]

*1: Pattern formation was not possible even at 1000mJ/cm ² .

It turns out that the photosensitive resin composition of the Example containing the photobase generator which satisfies the said general formula (1) is excellent in sensitivity, and it turns out that it is excellent in pattern formability although it is low-temperature curing conditions.

Claims (15)

1. A photosensitive resin composition is characterized in that, contains: the ionic photobase generator that the carboxylic acid shown in following general formula (1) and alkali form, In formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, at least one of X ₁ and X ₂ is an electron-withdrawing group, Y is an electron-donating group, B means base. 2 . The photosensitive resin composition according to claim 1 , characterized in that the molar absorptivity of the photobase generator is above 300 L·mol ⁻¹ ·cm ⁻¹ . 3. The photosensitive resin composition according to claim 1, characterized in that, in the general formula (1), the electron-withdrawing group is selected from the group consisting of -C≡N, -COCH ₃ , -NO ₂ , -F, The group consisting of -Cl, -Br and -I. 4. The photosensitive resin composition according to claim 1, characterized in that, in the general formula (1), the electron-donating group is selected from the group consisting of -CH ₃ , -C ₂ H ₅ , -CH(CH ₃ ) ₂ , the group consisting of -C(CH ₃ ) ₃ , -C ₆ H ₅ , -OH, -OCH ₃ and -OC ₆ H ₅ . 5. The photosensitive resin composition according to claim 1, further comprising a polymer precursor. 6. The photosensitive resin composition according to claim 5, wherein the polymer precursor is at least any one of polyamic acid and polyamic acid ester. 7. photosensitive resin composition according to claim 5, is characterized in that, described polymer precursor is the polyamic acid ester having the structure shown in following general formula (4-1), In formula (4-1), R ₇ is a tetravalent organic group, R ₈ is a group with an alicyclic skeleton, a phenylene group, a group with a diphenylene skeleton bonded with an alkylene group and any one of the alkylene groups, R _9-1 and R _10-1 are optionally the same or different from each other, a monovalent organic group or a functional group with silicon, R ₁₁ is a divalent organic group, m is An integer of 1 or more, and n is an integer of 0 or 1 or more. 8. The photosensitive resin composition according to claim ₇ , characterized in that, R in the general formula (4-1) is a quaternary fused ring comprising an aromatic ring and an aliphatic hydrocarbon ring. An organic group, a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a tetravalent organic group containing a fluorine atom. 9. The photosensitive resin composition according to claim 5, characterized in that, the polymer precursor has at least any of the following general formulas (4-1-1) and (4-1-2). A polyamic acid ester of the structure shown in one, _In the formula (4-1-1), R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group , R _9-1 and R _10-1 are optionally the same or different from each other, are a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, m is an integer of 1 or more, and n is 0 or an integer greater than 1, _In the formula (4-1-2), R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group , R _9-1 and R _10-1 are optionally the same or different from each other, are a monovalent organic group or a functional group having silicon, R ₁₁ is a divalent organic group, m is an integer of 1 or more, and n is 0 or an integer greater than 1. 10 . A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying it. 11 . 11. A cured product, characterized in that it is 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 circuit board comprising the cured product according to claim 11. 13. A photobase generator, characterized in that, it is the ionic type formed by carboxylic acid and alkali shown in the following general formula (1), In formula (1), R ₁ to R ₄ , X ₁ and X ₂ are each independently a hydrogen atom or a substituent, at least one of X ₁ and X ₂ is an electron-withdrawing group, Y is an electron-donating group, R ₁ to R ₄ are each independently a hydrogen atom or a substituent, and B represents a base. 14. The photobase generator according to claim 13, characterized in that, in the general formula (1), the electron-withdrawing group is selected from -C≡N, -COCH ₃ , -NO ₂ , -F, - A group consisting of Cl, -Br and -I. 15. The photobase generator according to claim 13 or 14, characterized in that, in the general formula (1), the electron donating group is selected from -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 .