TW201800845A - 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, hardened material, printed circuit board and photo-alkali generator

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

唑前驅物。 A method of chemically denaturing a resin by using a photobase generator that generates a base by the action of light is used in the fields of photoresist materials and photohardening materials. For example, Patent Document 1 describes a photosensitive resin composition characterized by containing a photobase generator composed of a salt of a carboxylic acid and a tertiary amine subjected to photodecarboxylation, a polyimide precursor, and / Or polybenzo

Azole precursor.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 4830435

It is required to improve the sensitivity of the photosensitive resin composition containing a photobase generator. If the sensitivity is improved, it is expected that even if the reaction conditions such as the conditions for light irradiation for generating alkali or the conditions for heat treatment during thermal curing using alkali are relaxed, the pattern can be patterned with good resolution. In addition, if the sensitivity is improved, it is expected that the reaction conditions as described above can be selected in a wide range, and the heat resistance of other materials such as the photosensitive resin composition or the base material coated with the photosensitive resin composition can be considered. After selecting properties such as properties, the most appropriate reaction conditions can be selected compared to the past. However, in the photobase generator described in Patent Document 1, which is a salt of a carboxylic acid and a tertiary amine that undergo photodecarboxylation, sufficient sensitivity cannot be obtained.

Therefore, 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 hardened product of the composition or a resin layer of the dry film, and a Printed circuit board and photosensitizer with excellent sensitivity.

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

That is, the photosensitive resin composition of this invention is characterized by containing the ionic type photobase generator of a carboxylic acid and a base represented by following General formula (1).

(式(1)中，R₁~R₄、X₁及X₂各自獨立為氫原子或取代基，X₁及X₂之至少一方為拉電子基，Y為給電子基，B表示鹼)。

(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, and B represents a base) .

The photosensitive resin composition of the present invention preferably has a Moire extinction coefficient of 300 L. mol ^-1 . cm ^-1 or more.

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

In the photosensitive resin composition of the present invention, it is preferred that 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 selected.

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

The photosensitive resin composition of the present invention is preferably such that the polymer precursor is at least one of polyamic acid and polyamic acid ester.

The photosensitive resin composition of the present invention is preferably such that the polymer precursor is a polyurethane having a structure represented by the following general formula (4-1).

(式(4-1)中，R₇為4價之有機基，R₈為以具有脂環式骨架之基、伸苯基、伸烷基所鍵結之具有伸聯苯基骨架之基、及、伸烷基中的任一者，R_9-1及R_10-1互相地可相同或不同為1價之有機基或具有矽之官能基，R₁₁為2價之有機基，m為1以上之整數，n為0或1以上之整數)。

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

In the photosensitive resin composition of the present invention, it is preferred that 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 A tetravalent organic group of 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 polymer precursor is a polyamide having a structure represented by at least one of the following general formulae (4-1-1) and (4-1-2). Acid ester.

(式(4-1-1)中，R₈為以具有脂環式骨架之基、伸苯基、伸烷基所鍵結之具有伸聯苯基骨架之基、及、伸烷基 中的任一者，R_9-1及R_10-1互相地可相同或不同為1價之有機基或具有矽之官能基，R₁₁為2價之有機基，m為1以上之整數，n為0或1以上之整數)。

(In the formula (4-1-1), R ₈ is a group having an alicyclic skeleton, a phenylene group, an alkylene group having a biphenylene group, and an alkylene group. Either, R _9-1 and R _10-1 may be the same or different from each other as 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 more).

(式(4-1-2)中，R₈為以具有脂環式骨架之基、伸苯基、伸烷基所鍵結之具有伸聯苯基骨架之基、及、伸烷基中的任一者，R_9-1及R_10-1互相地可相同或不同為1價之有機基或具有矽之官能基，R₁₁為2價之有機基，m為1以上之整數，n為0或1以上之整數)。

(In the formula (4-1-2), R ₈ is a group having an alicyclic skeleton, a phenylene group, an alkylene group having a biphenylene group, and an alkylene group. Either, R _9-1 and R _10-1 may be the same or different from each other as 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 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 the film.

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

The printed circuit board of the present invention is characterized by having the aforementioned hardened material.

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

(式(1)中，R₁~R₄、X₁及X₂各自獨立為氫原子或取代基，X₁及X₂之至少一方為拉電子基，Y為給電子基，B表示鹼)。

(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, and B represents a base) .

Light base generator of the present invention, the preferred system in the general formula (1), electron-withdrawing group is _{-C≡N, -COCH 3, -NO 2,} -F, -Cl, -Br, and, -I.

The photobase generator of the present invention is preferably an electron-donating group in the aforementioned general formula (1) as -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 .

According to the present invention, a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a hardened product of the composition or a resin layer of the dry film, and a printed circuit board having the hardened product can be provided. Photosensitizer with excellent sensitivity.

[Fig. 1] A graph showing the ¹ H-NMR spectrum of the photobase generator MONPA-TBD synthesized in Example 1-1. The horizontal axis represents a chemical shift ( δ ), and the vertical axis represents a relative intensity (ppm).

[FIG. 2] A graph showing the ¹ H-NMR spectrum of the photobase generator MONPA-DBU synthesized in Example 1-2. The horizontal axis represents a chemical shift ( δ ), and the vertical axis represents a relative intensity (ppm).

[Fig. 3] A graph showing the ¹ H-NMR spectrum of the photobase generator MONPA-2E4MZ synthesized in Example 1-3. The horizontal axis represents a chemical shift ( δ ), and the vertical axis represents a relative intensity (ppm).

[FIG. 4] A graph showing the ¹ H-NMR spectrum of the photobase generator MONPA-DBA synthesized in Examples 1-4. The horizontal axis represents a chemical shift ( δ ), and the vertical axis represents a relative intensity (ppm).

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

[Photo base 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.

(式(1)中，R₁~R₄、X₁及X₂各自獨立為氫原子或取代 基，X₁及X₂之至少一方為拉電子基，Y為給電子基，B表示鹼。在此，取代基係指氫原子以外之基)。

(In the 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, and B represents a base. Here, the substituent means a group other than a hydrogen atom).

The photobase generator has a structure in which an electron-drawing group and an electron-donating group are directly bonded to the meta and para positions of the benzene ring derived from phenylacetic acid, respectively. According to such a structure, an alkali can be produced.

Furthermore, with the above-mentioned structure, a photosensitizer having a high sensitivity can be produced even in i-line (365 nm). The molar extinction coefficient of the i-line of the aforementioned photobase generator is preferably 300L. mol ^-1 . cm ^-1 or more, more preferably 500L. mol ^-1 . cm ^-1 or more, more preferably 1100L. mol ^-1 . cm ^-1 or more. The higher the Moire extinction coefficient, the higher the sensitivity. Although the upper limit of the Moire extinction coefficient is not particularly limited, in terms of light stability or preservation stability, for example, 20,000L. mol ^-1 . cm ^-1 or less.

Furthermore, since the photobase generator is high in thermal decomposition temperature (Td), for example, the thermal stability when the coating film is dried is also excellent. The Td of the photo-alkali 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 a temperature when the weight loss ratio becomes 10%.

As the active light ray for the photo-alkali generator, visible light rays, ultraviolet rays, electron beams, X-rays, and the like can be irradiated, and ultraviolet rays are particularly preferably used, and particularly 248 nm, 365 nm, 405 nm, and 436 nm.

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 the substituent group include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silane group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, and a phosphine group. Radicals, phosphine radicals, phosphate radicals, phosphonium radicals, phosphonate radicals, alkoxy radicals, amidoamine radicals or organic radicals.

Here, the organic group refers to a group containing a carbon atom, for example, a group having a carbon number of 10 or less, and may have atoms other than carbon atoms (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine Atom, chlorine atom, etc.), etc.).

Although the electron-withdrawing group usable for X ₁ and X ₂ is not particularly limited, examples thereof include halogen atoms such as -C≡N, -COCH ₃ , -NO ₂ , and -F, -Cl, -Br, -I, and the like. . Among the drawn electron groups, -NO ₂ is preferred.

In addition, when only one of X ₁ and X ₂ is an electron-drawing group, the other is not particularly limited.

Although the electron-donating group usable by Y is not particularly limited, 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 these, -OCH _{3 is} preferred.

Although substituents usable for R ₁ and R ₂ are not particularly limited, examples thereof include an electron donating group. R ₁ and R ₂ are each preferably a hydrogen atom.

Although substituents usable for R ₃ and R ₄ are not particularly limited, examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silane group, a silanol group, a cyano group, a nitro group, a nitroso group, and a sulfinic acid group. Groups, sulfo groups, sulfonate groups, phosphine groups, phosphine groups, phosphino groups, phosphonate groups, or organic groups may be the same or different. R ₃ and R ₄ are each preferably a hydrogen atom.

In addition, R ₁ , R ₂ , X ₁ , X ₂ and Y preferably do not form a ring structure.

Although the base shown in B is not particularly limited, for example, amines (amine compounds) such as primary amines, secondary amines, and tertiary amines, nitrogen-containing cyclic compounds such as pyridine, hydrazine compounds, amidine compounds, and hydrogen can be used. Oxidation of quaternary ammonium salts, etc. Further, a base such as an amine disclosed in International Publication No. WO2009 / 19979 can also be used. Among the bases, secondary amines, tertiary amines, and nitrogen-containing cyclic compounds are preferred. The base shown by B is preferably a strong base.

Examples of the basic system include 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethyl-4-aminopyridine (DMAP), and 1-nitrogen as shown below. Heterobicyclo [2.2.2] octane (ABCO), 1,8-bis (dimethylamino) naphthalene (DMAN), 1,8-diazabicyclo [5.4.0] undec-7-ene ( DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1,1,3,3-tetramethylguanidine (TMG), 2-ethyl-4-methyl Imidazole (2E4MZ), piperidine (PPD), 1-ethyl-piperidine (EPPD), dibutylamine (DBA), 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), etc.

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

The aforementioned 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 those in formula (1).

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

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

Hereinafter, as a specific example of the photobase generator, a photoalkali generator adjusted with 4-methoxy-3-nitrophenylacetic acid (MONPA) and various bases is shown, but it is not limited thereto.

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

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

(Polymer precursor)

The photosensitive resin composition of the present invention contains a polymer precursor as a resin component capable of denaturing an alkali generated from the photo-alkali generator as a catalyst.

Examples of the polymer precursor system include, as a polyimide precursor, a polymer precursor having a repeating unit of polyamic acid or polyamic acid ester. Thing.

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

In the 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 hydroxyamidate group, an aromatic or aliphatic ester group, and an amine group. A base, a sulfonylamino group, a carbonate group, a silyl group, an alkylene oxide, a urethane group, an epoxy group, an oxetanyl group, and the like are used as constituent groups. Here, the organic group means a group containing a carbon atom.

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 10 to 1 million, 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 composed of an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably 4 to 20 carbon atoms, depending on the application. Selected from aliphatic groups. R ₇ and R _{8 are} preferably the acid dianhydrides described later and the substituents R ₇ and R ₈ included in the diamine used in the production of the polymer precursor.

When the photosensitive resin composition is patterned by short-wavelength light, it is preferable to use aliphatic groups as R ₇ and R ₈ from the viewpoint of the absorption characteristics of the polymer. In addition, for example, in the case where a fluorine-containing group is used as R ₇ and R ₈ , it is possible to improve the wavelength reduction and dielectric characteristics of light absorption.

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

In addition, although the valence of R ₇ only represents a valence for bonding with an acid, R ₇ may have a substituent. Similarly, although the bivalence of R ₈ only represents a valence for bonding with an amine, it 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 include alkyl, alkenyl, alkynyl, and aryl. When R ₉ and R ₁₀ are monovalent functional groups having silicon, examples thereof include a siloxy group, a silyl group, and a silanol group. Moreover, only a part of R ₉ and R ₁₀ may be hydrogen or a monovalent organic group, thereby controlling the solubility.

As the polymer precursor system, polyamines such as R ₉ and R _{10 each} having a hydrogen atom are suitably used. Thereby, alkali developability becomes favorable, and a favorable pattern can be obtained.

(Polyamic acid)

Polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared by mixing only an acid dianhydride and a diamine in a solution. can The first-stage reaction is synthesized, and it is easily and inexpensively obtained without further modification, so it is suitable for use. Although the method for synthesizing the polymer precursor is not particularly limited, a known method can be applied.

Examples of the tetracarboxylic dianhydride usable in the present invention include those represented by the following general formula (5). However, the specific example shown below is an example, and a well-known person can be used as long as it is not contrary to the meaning of this invention.

(式中之R₇係如上述)。

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

Further, the present embodiment polyamide repeating units in the acid form of the R ₇ group, the preferred system is used as a raw material from the polyamide acid produced tetracarboxylic dianhydride of R _7.

Examples of the acid dianhydride systems that can be used in the production of the above polymer precursors include 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3). -Furan) naphthalene [1,2-c] furan-1,3-dione, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetra Carboxylic dianhydride, cyclopentane tetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ', 4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylketone tetracarboxylic dianhydride, 2,3', 3,4'-diphenylketone 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-dicarboxylic acid Phenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxybenzene Hydrazone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxybenzene 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) benzidine] phthalic anhydride, 1,4- Bis [(3,4-dicarboxy) benzidine] 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] phenyl} ketone dianhydride, 4,4'-bis [4- (1,2-dicarboxy) phenoxy ] Biphenyl dianhydride, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy ] Phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) benzene Oxy] phenyl} fluorene dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} fluorene 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] benzene } -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro -2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetra Carboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfofluorenyl diphthalic anhydride, m-bitriphenyl-3,3 ', 4,4'-tetracarboxylic Aromatic tetracarboxylic acids such as acid dianhydride, p-bitriphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride Dianhydride, etc.

These are used alone or in combination of two or more. Next, as a particularly suitable tetracarboxylic dianhydride system, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furan) naphthalene [ 1,2-c] furan-1,3-dione, pyromellitic dianhydride, 3,3 ', 4,4'-diphenylketone 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 fluorinated acid dianhydride or an acid dianhydride having an alicyclic skeleton is used as the acid dianhydride used in combination, physical properties such as solubility and thermal expansion coefficient can be adjusted without impairing transparency. If rigid acid dianhydrides such as pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride are used, The linear thermal expansion coefficient of the finally obtained polyimide will decrease, but since it tends to hinder the improvement of transparency, it can be used together while paying attention to the copolymerization ratio.

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

Examples of the amines usable in the present invention include diamines represented by the following general formula (6). However, the following is an example, and a well-known person may be used as long as it does not violate the purpose of the present invention.

H ₂ NR ₈ -NH ₂ (6) (wherein R ₈ is as described above).

Examples of the diamine in the case where the R ₈ 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 '-Diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenylphosphonium, 3 , 3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-amine Phenylphenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, 4,4'-bis (4-aminophenoxy) biphenyl, 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, m-phenylenediamine, 4,4'-diaminodiphenyl ether , 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene.

Examples of the diamine in the case where the R ₈ group is a divalent aliphatic group include 1,1-m-xylenediamine, 1,3-propanediamine, tetramethylenediamine, and glutaric acid. Amine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, 4,4-diaminoheptanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrobicyclo Pentadienyl diamine, hexahydro-4,7-methylindenyl dimethylene diamine, tricyclic [6.2.1.02,7] -undecene dimethyl diamine, 4, 4'-methylenebis (cyclohexylamine), isophoronediamine.

In addition, as another example, a diamine polysiloxane represented by the following general formula (11) can be mentioned.

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

Specifically, examples of the R ₂₈ and R ₂₉ in the formula (11) include carbons of 1 to 7 carbons such as methylene, ethylene, and propyl, and carbons of phenyl and the like. number arylene group having 6 to 18, R ₃₀ and R ₃₁ as lines include: methyl, ethyl, etc. the alkyl group having 1 to 7 carbon atoms, a phenyl group, etc. and the like carbon atoms, an aryl group having 6 to 12.

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

For example, an acid anhydride such as 3,3'-diphenyl ketone tetracarboxylic dianhydride is reacted with an alcohol such as ethanol to form a half ester. This half ester was made into diester diacid chloride using thionyl chloride.

By reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid, a polyamic acid ester can be obtained.

As the photosensitive resin composition, at least a part of the polymer precursor system having a repeating unit of polyamic acid or polyamic acid ester may use a single type of material, or a plurality of types may be used as a mixture. In addition, at least one of R ₇ and R ₈ may be a copolymer formed by a plurality of structures, respectively.

In addition, a polyimide can also be obtained by reacting a half ester obtained by reacting the above-mentioned acid anhydride with an alcohol with a diisocyanate such as isofluoroketone diisocyanate. In addition, a synthetic method using a diisocyanate can more easily synthesize a polyamidate than a synthetic method using the diamine described above.

As a diisocyanate system which can be used for obtaining a polyamidate, the diisocyanate represented by following General formula (7) is mentioned.

However, the following is an example, and a well-known person may be used as long as it does not violate the purpose of the present invention.

OCN-R ₈ -NCO (7) (wherein R ₈ is as described above).

Examples of the diisocyanate system include, for example, isophorone diisocyanate (ITI), toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), and 2,2-bis (4 -Isocyanatophenyl) hexafluoropropane, Hexamethylene diisocyanate (HMDI) and the like.

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

(式(4-1)中，與前述通式(4)相同地，R₇為4價之有機基，R₈為2價之有機基，R₁₁為2價之有機基，m為1以上之整數，n為0或1以上之整數。R_9-1及R_10-1係互相地可相同或不同為1價之有機基或具有矽之官能基。

(In the formula (4-1), similarly to the aforementioned general formula (4), R ₇ is a tetravalent organic group, R ₈ is a divalent organic group, R ₁₁ is a divalent organic group, and m is 1 or more. Integer, n is an integer of 0 or 1. R _9-1 and R _10-1 may be the same or different from each other as a monovalent organic group or a functional group having silicon.

R _{8 is} preferably a group having an alicyclic skeleton, a group having a phenylene group, an phenylene group bonded with an phenylene group, and a group having an phenylene group, and an alkylene group).

In the 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 an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, and 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 aforementioned general formula (5) used in the production of the polymer precursor.

Polyurethane having a structure represented by the aforementioned general formula (4-1), and particularly from the viewpoint of resolution, R _{7 is} preferably 4 which is a condensed ring containing an aromatic ring and an aliphatic hydrocarbon ring. Valent organic 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 a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthyl group, especially a phenyl group), and more preferably has a trifluoromethyl group and an aromatic group.

The polyamidate having a structure represented by the aforementioned general formula (4-1) is preferably represented by at least one of the following general formulae (4-1-1) and (4-1-2) Of the structure.

(式(4-1-1)中，R₈、R_9-1、R_10-1、R₁₁、m及n係與式(4-1)相同)。

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

(式(4-1-2)中，R₈、R_9-1、R_10-1、R₁₁、m及n係與式(4-1)相同)。

(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 one of a group having an alicyclic skeleton, a group having a phenylene skeleton, an phenylene skeleton bonded with an phenylene group, and an alkylene group. . The aforementioned phenylene and alkylene systems are directly bonded to two nitrogen atoms bonded to R ₈ in Formula (4-1), respectively. On the other hand, the above-mentioned alicyclic skeleton and the above-mentioned phenylene skeleton bonded by the above-mentioned alkylene are directly bonded to two nitrogen atoms bonded to R ₈ in formula (4-1), It may not be directly bonded. 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 radical having the aforementioned alicyclic skeleton at R ₈ may have a substituent or may form a condensed ring. The group having the alicyclic skeleton is preferably represented by the following general formula (8A).

(式(8A)中，n1係表示0~10之整數，R_8A1係表示脂肪族基，較佳為碳數1~5之伸烷基，更佳為亞甲基，R_8A2各自獨立表示脂肪族基或芳香族基，較佳為甲基、乙基等之脂肪族基)。

(In formula (8A), n1 represents an integer from 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 each independently represents a fat A group or an aromatic group is preferably an aliphatic group such as a methyl group or an ethyl group).

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

(式(8B)中，n2係表示0~4之整數，R_8B1係各自獨立表示脂肪族基或芳香族基，較佳為甲基、乙基等之脂肪族基)。

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

The radical system having a biphenyl group having the aforementioned alkylene bond at R ₈ may have a substituent or may form a condensed ring. The group having an extended biphenyl group bonded by the above-mentioned alkylene group is preferably represented by the following general formula (8C).

(式(8C)中，n3及n4係各自獨立表示0~4之整數，R_8C1及R_8C2係各自獨立表示脂肪族基或芳香族基，較佳為甲基、乙基等之脂肪族基，R_8C3係表示碳數1~5之伸烷基)。

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

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

The aforementioned alkylene group at 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. The aforementioned alkylene group at R ₈ may have a substituent such as an aliphatic group or an aromatic group.

R ₈ is a group having an alicyclic skeleton because of excellent resolution, and 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 the formula (4-1) are each independently a monovalent organic group or a functional group having silicon. Examples of the monovalent organic group based on R _9-1 and R _10-1 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Examples of the monovalent functional group having silicon in R _9-1 and R _10-1 include a siloxy group, a silyl group, and a silanol group.

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

In the present invention, R ₁₁ in (4-1) is a divalent organic group, and examples thereof include aromatic or aliphatic ester groups, amido groups, amido amido imino groups, siloxane groups, An epoxy group, an oxetanyl group, or the like constitutes at least a part of a constituent group.

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

The solvent system that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it dissolves the photobase generator, the polymer precursor, and other additives.

Examples include N, N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamidamine, Ethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetamidine-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N- Cyclohexyl-2-pyrrolidone, dimethyl sulfene, hexamethylphosphoramidine, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. These systems can be used alone or in combination. The above is mixed. Although the amount of the solvent used is not particularly limited, for example, it may be used in a range of 50 to 9000 parts by mass relative to 100 parts by mass of the polymer precursor in accordance with the thickness or viscosity of the coating film.

唑、2-(p-二甲基胺基苯乙烯基)苯并噻唑、2-(p- 二甲基胺基苯乙烯基)萘(1,2-d)噻唑、2-(p-二甲基胺基苯甲醯)苯乙烯等，就感度的點而言，較佳係使用4-(1-甲基乙基)-9H-硫

-9-酮等之噻噸酮類。此等係可單獨或者2~5種之組合使用。增感劑，較佳係相對於高分子前驅物100質量份，使用0.1~10質量份。 A sensitizer may be added to the photosensitive resin composition of the present invention in order to further improve the light sensitivity. Examples of the sensitizer include: Michler's ketone, 4,4'-bis (diethylamino) diphenyl ketone, and 2,5-bis (4'-diethylamino) Benzylidene) 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 (chalcone), 4,4'-bis (diethylamino) chalcone, p-dimethylaminobenzylideneindene, p-dimethylaminobenzylideneindone, 2 -(p-dimethylaminophenylphenylphenyl) -benzothiazole, 2- (p-dimethylaminophenylphenylene) benzothiazole, 2- (p-dimethylaminobenzene Vinylidene) isonaphthiazole, 1,3-bis (4'-dimethylaminobenzylidene) acetone, 1,3-bis (4'-diethylaminobenzylidene) acetone, 3,3 '-Carbonyl-bis (7-diethylaminocoumarin), 3-acetamidine-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Dioxin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethyl Aminocoumarin, N- Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholine diphenyl ketone, dimethylamino isobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) Benzo

Azole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphthalene (1,2-d) thiazole, 2- (p-bis Methylaminobenzyl) styrene and the like, in terms of sensitivity, it is preferable to use 4- (1-methylethyl) -9H-sulfur

Thioxanthone such as -9-one. These systems can be used alone or in a combination of 2 to 5 types. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the polymer precursor.

Moreover, in the photosensitive resin composition of this invention, you may add an adhesion adjuvant in order to improve adhesiveness with a base material. A well-known thing can be used as an adhesion adjuvant, as long as it does not violate the meaning of this invention. Examples include: γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyl Methyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N- [3- (triethoxysilyl) propyl] phthalic acid, diphenylketone tetra Reaction products of carboxylic dianhydride and (triethoxysilyl) propylamine. The blending amount of the auxiliary is preferably in the range of 0.5 to 10 parts by mass relative to 100 parts by mass of the polymer precursor.

Moreover, you may add an alkali proliferation agent to the photosensitive resin composition of this invention. When forming a pattern of a thick film, the decomposition rate of the photo-alkali generator from the surface to the same level is required. In this case, in order to increase sensitivity, it is preferable to add an alkali multiplying agent. For example, an alkali multiplier disclosed in Japanese Patent Application Laid-Open No. 2012-237776, Japanese Patent Application Laid-Open No. 2006-282657, and the like can be used.

In addition, in the photosensitive resin composition of the present invention, other photosensitive components that generate an acid by light may be added within a range that does not significantly impair the film properties after curing. Photosensitive resin in the present invention When a compound having one or more ethylenically unsaturated bonds is added to the composition, a photo radical generator may be added.

In order to impart processing characteristics or 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, microparticles, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silicon dioxide, carbon, and layered silicate, and the like, and these may also have a porous or hollow structure. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, and fibers.

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).

In the formation of the dry film, the photosensitive resin composition of the present invention can be diluted with the above-mentioned organic solvent to adjust the appropriate viscosity, and can be applied by a spot coater, a knife coater, a lip coater, or a bar coater. A cloth machine, an extrusion coater, a reverse coater, a transfer roll coater, a groove roll coater, and a sprayer are applied on a carrier film to apply a uniform thickness. Thereafter, the applied photosensitive resin composition is dried at a temperature of usually 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. Although the coating film thickness is not particularly limited, in general, the film thickness after drying is appropriately selected within a range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film can be used, preferably a polyester film such as polyethylene terephthalate, a polyimide film, or a polyimide film. Plastic film such as amine, imine film, polypropylene film, polystyrene film, etc. Although the thickness of the carrier film is not particularly limited, in general, it is appropriately selected within a range of 10 to 150 μm.

After forming a resin layer composed of the photosensitive resin composition of the present invention on a carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. As the peelable cover film system, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As the cover film, when the cover film is peeled off, it may be smaller than the adhesion between the resin layer and the carrier film.

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

First, as step 1, a photosensitive resin composition is applied to a substrate and dried to obtain a coating film. As a method for applying a photosensitive resin composition to a substrate, a method conventionally used for coating a photosensitive resin composition can be used. For example, a spin coater, a bar coater, and a doctor blade can be used. A coating method such as a coater, a curtain coater, a screen printing machine, a spray coating method using a spray coater, and an inkjet method. As a drying method of a coating film, methods, such as air-drying, heat-drying by an oven or a hot plate, and vacuum drying, can be used. In addition, the drying of the coating film is preferably performed under conditions that avoid sulfonation of polyimide in the photosensitive resin composition. Specifically, it can be 20 ℃ ~ 140 ℃, natural drying, air drying, or heating drying under the conditions of 1 minute to 1 hour. Preferably, it is dried on a hot plate for 1 to 20 minutes. In addition, vacuum drying may be performed, and in this case, it may be performed at room temperature under conditions of 1 minute to 1 hour.

There are no particular restrictions on the substrate, and silicon wafers, circuit substrates, various resins, metals, and passivation protection films for semiconductor devices can be widely used.

In addition, because it can be imidized at low temperature, it can be widely used for components and materials that are not suitable for high temperature processing such as substrates of printed circuit boards.

Next, as step 2, the coating film is exposed through a photomask having a pattern, or is directly exposed. Exposure to light is one that uses a wavelength that activates a photobase generator to generate a base. As described above, if an appropriate sensitizer is used, the light sensitivity can be adjusted. As the exposure device, contact calibration, projection, step exposure, and direct laser exposure devices can be used.

Next, as step 3, heating is performed so that the imidization of the coating film is promoted by the alkali generated in the coating film. As a result, in step 2 described above, the alkali generated in the exposure unit becomes a catalyst, and the polyfluorinated ester is partially imidized. The heating time and heating temperature are appropriately changed depending on the type of the polyamidate used, the thickness of the coating film, and the type of the photobase generator. Typically, when the thickness of the coating film is about 10 μm, it is performed at 110 to 200 ° C. for about 2 to 10 minutes. If the heating temperature is too low, partial imidization cannot be efficiently achieved. On the other hand, if the heating temperature is too high, the imidization of the unexposed portion proceeds, resulting in the dissolution of the exposed portion and the unexposed portion. The difference in resolution is reduced, and there are doubts that hinder pattern formation.

Next, as step 4, the coating film is processed with a developing solution. Thereby, a pattern film composed of polyfluorene ester and partially fluorinated polyfluorene can be formed on the substrate.

As a method used for development, any method may be selected from conventionally known development methods of photoresist, for example, a rotary spray method, a paddle method, and an immersion method with ultrasonic treatment. Examples of the developing liquid system include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethyl Aqueous solutions of quaternary ammonium salts such as ammonium hydroxide and tetrabutylammonium hydroxide. In addition, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant may be used as an aqueous solution in accordance with need. Thereafter, if necessary, the coating film is washed with a cleaning solution to obtain a pattern film. As the cleaning liquid system, distilled water, methanol, ethanol, isopropyl alcohol, or the like can be used alone or in combination.

Moreover, as a developing solution, for example, N-methyl-2-pyrrolidone, N-acetam-2-pyrrolidone, N, N-dimethylformamidine, N, N-di Methylacetamide, dimethylmethane, γ-butyrolactone, hexamethylphosphortriamide, methanol, ethanol, isopropanol, methylcarbitol, ethylcarbitol, toluene, xylene , Ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate Organic solvents such as esters and diacetone alcohol.

Thereafter, as step 5, the patterned film is heated. The heating temperature is appropriate so that the patterned film of polyimide can be cured. set up. For example, in an inert gas, heating is performed at 150 to 300 ° C for about 5 to 120 minutes. The more preferable range of the heating temperature is 150 to 250 ° C, and the 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 type oven with a settable temperature program. As the environment (gas) at this time, air may be used, and an inert gas such as nitrogen or argon may be used.

The use of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include printing inks, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, building materials, three-dimensional shaping, and optics. Various fields and products using resin materials are known for parts and the like. It is particularly suitable for use in a wide range of fields / products where properties such as heat resistance, dimensional stability, and insulation properties of polyimide films are effective, for example, coatings or printing inks, or color filters, and flexible displays. Films, semiconductor devices, electronic parts, interlayer insulation films, solder resists, circuit forming films, optical circuits, optical circuit parts, anti-reflection films, three-dimensional images, optical components or building materials.

In particular, in the case where 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 (resistor), and the pattern film formed by this is Functions as a component that imparts heat resistance or insulation as a permanent film made of polyimide. For example, it is suitable for forming color filters, films for flexible displays, electronic parts, semiconductor devices, and interlayer insulation. Film, solder resist or cover film, wiring coating film, solder dam, optical circuit, optical circuit part, anti-reflection film, other optical components or electronic components Pieces.

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

The 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 formulae (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 aforementioned base system, it can be used for the base represented by B in the aforementioned general formula (1).

The mixing of the carboxylic acid and the base is preferably performed by dropping a solution of the base in a solution of the carboxylic acid in a light-shielding manner.

Examples

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, in the following contents, as the "part" and "%", unless otherwise specified, they are all based on quality.

[Synthesis of carboxylic acid] (Reference Synthesis Example 1: Synthesis of 4-methoxy-3-nitrophenylacetic acid (MONPA))

In a 500 ml two-necked eggplant-type flask, 30 ml of concentrated nitric acid (67% by mass) and 4.32 g (20.0 mmol) of 4-methoxyphenylacetic acid (MOPA) were mixed and stirred at room temperature (room temperature, 6 h). ). The obtained mixture was dropped into cold water, followed by 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, product Rate: 60%).

[Synthesis of photobase generator] (Example 1-1, Synthesis of MOMPA-TBD)

In a 50 ml eggplant-type flask, 0.300 g (1.42 mmol) of 4-methoxy-3-nitrophenylacetic acid (MONPA) synthesized above and dissolved in 10 ml of dry ethanol were dissolved in 10 ml of dry ethanol. 0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) was mixed and stirred overnight at room temperature. The obtained mixture was concentrated and reprecipitated with EtOH / Et ₂ O to obtain MOMPA-TBD (yield: 0.289 g, yield: 58%) as an orange viscous liquid. The graph of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 1, and the analysis result of the peak is 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 ), 7.0 (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)

Changed 1,98,3-diazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 to 1.98-diazabicyclo [5.4.0] Eleven-7-ene (DBU) was 0.216 g (1.42 mmol), except that in the same manner as in Synthesis Example 1, MOMPA-DBU (yield: 0.419 g, yield: 81%). The graph of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in the second graph, and the analysis result of the peak is shown below.

δ 1.6-1.8 (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)

0.198 g (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 was changed to 2-ethyl-4-methylimidazole (2E4MZ) Except for 0.156 g (1.42 mmol), MOMPA-2E4MZ (yield: 0.186 g, yield: 41%) was obtained in the same manner as in Synthesis Example 1 as an orange viscous liquid. The graph of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in Fig. 3, and the analysis result of the peak is shown below.

δ1.12 (t, J = 7.6Hz, 6H, -CH ₂ CH ₃ ), 2.15 (s, 3H, -CH ₃ ), 2.65 (q, J = 7.6H, 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)

1.98,1 (1.42 mmol) of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) in Synthesis Example 1 was changed to 0.184 g (1.42 mmol) of dibutylamine (DBA) Except for the above, in the same manner as in Synthesis Example 1, MOMPA-DBA (yield: 0.473 g, yield: 98%) was obtained as an orange solid. The graph of ¹ H-NMR (300 MHz, CDCl ₃ ) is shown in FIG. 4, and the analysis result of the peak is shown below.

δ 0.86 (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 a 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 charged into a flask, heated at 50 ° C, and slowly charged into cyclohexane Until the ketoprofen is completely dissolved with 1,4-diazabicyclo [2.2.2] octane. Thereafter, when cooled, 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 Extinction Coefficient of Photobase Generator]

For each of the photobase generators synthesized above, MultiSpec-1500 manufactured by Shimadzu Corporation was used to measure the UV-vis spectrum, and the Moire extinction coefficient of i-line (365 nm) was measured. The solution unit was made of quartz and had a light path of 1 cm. In addition, the Moire extinction coefficient is obtained by dividing the extinction of the solution. The value of the thickness of the light absorbing layer and the molar concentration of the solute. The results are shown in Table 1.

It is known that the photo-alkali generators of Examples 1-1 to 1-4 satisfying the aforementioned general formula (1) have high Moire extinction coefficients of the i-line.

[Evaluation of Heat Resistance of Photo-Alkali Generator]

The photo-alkali generator (MONPA-TBD) of Example 1-1 was measured for TG-DTA (temperature rise rate: 5 ° C./min) using Mac and TG-DTA2000S manufactured by Science Corporation.

[Synthesis of Polyurethane] (Synthesis example 1: Synthesis of polyamidate A-1)

To 5 g of 6FDA (4,4 '-(hexafluoroisopropylidene) diphthalic anhydride) as an acid dianhydride, about 25 g of dry tert-butyl alcohol was added and refluxed. Approximately 30 minutes after the start of reflux, a substantially transparent liquid was obtained. 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. Drying under reduced pressure completely removed tert-butyl alcohol, and the half ester of the acid anhydride described in Table 1 was obtained as white crystals.

In a three-necked flask with a capacity of 100 ml, add the acid anhydride described in Table 1. After dissolving 5 mmol of a half-ester and 0.0125 mmol of anhydrous 3-methyl-1-phenyl-2-phospholene 1-oxide, the solution was dissolved in 10 ml of dehydrated cyclobutane with nitrogen flowing. 5 mmol of anhydrous ITI (isofluoroketone diisocyanate) as a diisocyanate was dissolved in 5 ml of dehydrated cyclobutane, and the solution was dropped into 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 precipitate-containing liquid 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 carried out to prepare a 15% by mass solution of poly (urethane) A-1 using dehydrated DMAc as a solvent.

(Synthesis example 2: Synthesis of polyamidate A-2)

Changed 6FDA as acid dianhydride to TDA (1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furan) naphthalene [1,2-c ] Furan-1,3-dione), except for the same manner as in Synthesis Example 1, a polyurethane A-2 solution was prepared.

(Synthesis Example 3: Synthesis of Polyamidate 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-methylpyrrole 30 g of pyridone (NMP) was stirred at 60 ° C. for 4 hours, and then stirred at room temperature overnight to obtain polyamic acid. To this was added 9.45 g of trifluoroacetic anhydride under water cooling, and the mixture was stirred at room temperature for 3 hours, and 1.73 g of ethanol was added. This reaction solution was dropped into distilled water, and the precipitate was filtered, collected, and dried under reduced pressure to prepare a solution of polyamidate A-3. The number average molecular weight of the polyamidate A-3 was 27,000.

(Example 2-1)

Based on the blending ratio (mass ratio) described in the following table, a photobase generator was added to the polyamine solution obtained above to dissolve it, and the photosensitive resin compositions of Examples and Comparative Examples were obtained. . In addition, the blending amount of the polyamidate in the table indicates the amount of solid content.

On a 4-inch silicon wafer, the photosensitive resin composition of Example 2-1 in the following table was applied by spin coating, and heated on a hot plate at 80 ° C for 20 minutes to form a 10 μm-thick film. A photosensitive resin composition film. This film was exposed by a high-pressure mercury lamp exposure device equipped with an i-line filter through a mask pattern at a light amount ranging from 0 to 1000 mJ / cm ² . After exposure, heating was performed on a hot plate at 140 ° C. for 10 minutes, and then immersed in a developing solution in which a 2.38% aqueous solution of tetramethylammonium hydroxide and 2-propanol was mixed at a weight ratio of 1: 1 for 90 seconds , And further washed with water for 20 seconds, thereby performing pattern development.

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

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

Using the same procedure as in Example 2-1, a development test was performed with the blending ratio (mass ratio) and exposure amount described in the following table, and the exposure amount for pattern formation was confirmed.

It was found that the examples of the photosensitive resin composition containing the photobase generator satisfying the aforementioned general formula (1) had excellent sensitivity, and although the curing conditions were low temperature, the pattern forming property was also excellent.

Claims (15)

A photosensitive resin composition characterized by containing an ionic photobase generator of a carboxylic acid and a base represented by 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, and B represents a base) . For example, the photosensitive resin composition of claim 1, wherein the molar extinction coefficient of the photo-alkali generator is 300L. mol ^-1 . cm ^-1 or more. The photosensitive resin composition according to claim 1, wherein in the general formula (1), the electron-withdrawing group is -C≡N, -COCH ₃ , -NO ₂ , -F, -Cl, -Br, and- I selected from the group. The photosensitive resin composition according to claim 1, wherein in the aforementioned 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 selected. The photosensitive resin composition according to claim 1, further comprising a polymer precursor. The photosensitive resin composition according to claim 5, wherein the polymer precursor is at least one of polyamic acid and polyamic acid ester. The photosensitive resin composition according to claim 5, wherein the polymer precursor is a polyurethane having a structure represented by the following general formula (4-1),

(In the formula (4-1), R ₇ is a tetravalent organic group, and R ₈ is a group having an phenylene skeleton bonded by a group having an alicyclic skeleton, phenylene, and alkylene, And R _9-1 and R _10-1 may be the same or different from each other as 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 an integer of 0 or 1 or more). For example, the photosensitive resin composition of claim 7, wherein 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 containing an aromatic group, and A tetravalent organic group of an alicyclic hydrocarbon group or a tetravalent organic group containing a fluorine atom. The photosensitive resin composition according to claim 5, wherein the polymer precursor is a polyamide having a structure represented by at least one of the following general formulae (4-1-1) and (4-1-2) Acid ester,

(In the formula (4-1-1), R ₈ is a group having an alicyclic skeleton, a phenylene group, an alkylene group having a biphenylene group, and an alkylene group. Either, R _9-1 and R _10-1 may be the same or different from each other as 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 more);

(In the formula (4-1-2), R ₈ is a group having an alicyclic skeleton, a phenylene group, an alkylene group having a biphenylene group, and an alkylene group. Either, R _9-1 and R _10-1 may be the same or different from each other as 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 more). A dry film characterized by having a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the film. A cured product obtained by curing a photosensitive resin composition according to any one of claims 1 to 9 or a resin layer of a dried film according to claim 10. A printed circuit board characterized by having a hardened body as claimed in claim 11. A photobase generator characterized by the ionic form 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, at least one of X ₁ and X ₂ is an electron-withdrawing group, Y is an electron-donating group, and R ₁ to R ₄ are each independently a hydrogen atom or a substituent, and B represents a base). The photobase generator according to claim 13, wherein in the aforementioned general formula (1), the electron-drawing group is -C≡N, -COCH ₃ , -NO ₂ , -F, -Cl, -Br, and -I Selected from the group. The requested item 13 or 14 of the optical base generator, wherein the general formula (1), the electron-donating group by _{-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 selected.