JP2009265294A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyimide resin composition curable at a low temperature. <P>SOLUTION: The photosensitive resin composition contains: a photo-base generator (A) which is at least one kind of a compound selected from a group composed of benzophenone compounds (A1) expressed by a general formula (1), specified anthraquinone compounds (A2) and specified coumarin compounds (A3), and generates a base by irradiation with actinic rays; and a polyimide precursor (B). In the general formula (1), R<SB>1</SB>to R<SB>10</SB>are selected from a group composed of hydrogen atoms, halogen atoms, alkoxy groups (with 1 to 20 carbon atoms), nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, silyl groups (with 1 to 20 carbon atoms), acyl groups (with 1 to 20 carbon atoms), amino groups, cyano groups, alkyl groups (with 1 to 20 carbon atoms), phenyl groups and naphthyl groups. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition having excellent low-temperature curability.

  In recent years, application of a polyimide resin, which is a high heat-resistant resin, has been studied as a material used for a semiconductor interlayer insulating film, a protective film, and the like. This is for high integration, multi-layering, high reliability, etc. of semiconductor components.

  When a photosensitive polyimide is applied to a semiconductor interlayer insulating film, a protective film, etc., it is important to sufficiently imidize the polyimide precursor in order to develop the original mechanical properties, thermal properties, etc. of the polyimide. In order to achieve sufficient imidization, it is described that the developed coating film is heated in a high temperature (for example, 350 ° C. or higher) environment. (Patent Document 1)

In recent years, semiconductor components (FeRAM, magnetoresistive memory, etc.) that cannot withstand the high temperature (eg, 350 ° C.) processes necessary to achieve sufficient imidization have been developed. In addition, there is a concern that the circuit wiring and the like have a higher definition and the yield of the circuit wiring and the like is reduced due to the high temperature process. In addition, due to the multi-layered and complexed chips, high temperature processes are repeatedly performed, and there is a concern that the yield will be further reduced.

When a polyimide film is used as a semiconductor surface protective film, stress is generated at the interface due to a difference in thermal shrinkage between the semiconductor and the polyimide film when returning from a high temperature to room temperature, which may cause cracks in the polyimide film. Accordingly, it is preferable to set the heating temperature necessary to develop the original mechanical properties and thermophysical properties of the polyimide as low as possible.
In recent years, various photobase generators that generate amines upon exposure to actinic rays have been proposed. (For example, Patent Document 2, Patent Document 3, Patent Document 4, Non-Patent Document 1)
JP-A-5-197148 JP 2007-119766 A JP 2007-262276 A JP 2006-282880 A Macromolecules A.M. Mochizuki, Vol. 28, no. 1,1995

When the above photobase generator is applied to photosensitive polyimide, it is insufficient from the viewpoint of achieving sufficient imidization at a low temperature.
The problem to be solved by the present invention is to provide a photosensitive polyimide resin composition that cures at a low temperature.

The present inventors diligently studied to solve the above problem and arrived at the present invention. That is, the present invention is at least selected from the group consisting of the compound (A1) represented by the general formula (1), the compound (A2) represented by the general formula (2), and the compound (A3) represented by the general formula (3). 1 type of compound, Comprising: The photobase generator (A) which generate | occur | produces a base by irradiation of actinic light, and the photosensitive resin composition characterized by containing a polyimide precursor (B).
(Substituents R _{1 to} R ₁₀ are hydrogen atom, halogen atom, alkoxy group (1 to 20 carbon atoms), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1 to 20 carbon atoms), acyl group (carbon Selected from the group consisting of an amino group, a cyano group, an alkyl group (1 to 20 carbon atoms), a phenyl group, and a naphthyl group, provided that any _{one of} substituents R _{1 to} R ₁₀ is It is a substituent represented by the general formula (4).)
(Substituents R _{1 to} R ₈ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl group (carbon Selected from the group consisting of an amino group, a cyano group, an alkyl group (1 to 20 carbon atoms), a phenyl group, and a naphthyl group, provided that any _{one of} substituents R _{1 to} R ₈ is It is a substituent represented by General formula (4).
(Substituents R _{1 to} R ₆ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl group (carbon Selected from the group consisting of an amino group, a cyano group, an alkyl group (having 1 to 20 carbon atoms), a phenyl group, and a naphthyl group, provided that at least one of the substituents R _{1 to} R ₆ is general. It is a substituent represented by Formula (4).
(Substituents R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. M represents an integer of 2 to 4. X ⁻ represents an anion. C ^* represents carbon at a substituted site. .)

The photosensitive resin composition of this invention has an effect that a polyimide is obtained by a low-temperature process.

BEST MODE FOR CARRYING OUT THE INVENTION

The photosensitive resin composition of the present invention contains a photobase generator (A) and a polyimide precursor (B).
The photobase generator (A) is composed of a compound (A1) represented by the general formula (1), a compound (A2) represented by the general formula (2), and a compound (A3) represented by the general formula (3). It is at least one compound selected from the above.
The base contained in the substituent represented by the general formula (4) is generated by cleaving the bond portion between the photobase generator (A) and the substituent represented by the general formula (4) by actinic rays. .
The weight percent of the photobase generator (A) relative to the weight of the photobase generator (A) and the polyimide precursor (B) is preferably 1 wt% to 40 wt%, more preferably 5 wt% to 30 wt%, Particularly preferred is 10 to 20% by weight.

First, the compound (A1) represented by the general formula (1) contained in the photosensitive resin composition of the present invention will be described. (A1) of the present invention is a compound having a benzophenone skeleton, which is an example of a compound having a maximum absorption wavelength near i-line (365 nm). Substituents R _{1 to} R ₁₀ are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc. For example, a hydrogen atom, a halogen atom, an alkoxy group (carbon number) 1-20), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1-20 carbon atoms), acyl group (1-20 carbon atoms), amino group, cyano group, alkyl group (1-20 carbon atoms) ), A functional group selected from the group consisting of a phenyl group and a naphthyl group. However, any _{one of} the substituents R _{1 to} R ₁₀ is a substituent represented by the general formula (4).

Examples of the alkoxy group (having 1 to 20 carbon atoms) include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, a pentyloxy group, an iso-pentyloxy group, and neo. -Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like. Examples of the silyl group (having 1 to 20 carbon atoms) include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

Examples of the acyl group (having 1 to 20 carbon atoms) include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, cyclohexylcarbonyl group and the like.
Examples of the alkyl group (having 1 to 20 carbon atoms) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and iso-pentyl. Group, neo-pentyl group, hexyl group, heptyl group, octyl group and the like.
The halogen atom is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.

Preferred examples of the substituent include a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, a phenyl group, and carbon. Examples thereof include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and an acyl group having 1 to 15 carbon atoms. Particularly preferred are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The alkyl moiety may be linear, branched or cyclic.

The general formula (4) will be described. The general formula (4) is a compound having an amidine skeleton, and m is an integer of 2 to 4. Particularly preferred are 1,8-diazabicyclo [5.4.0] -7-undecene in which m is 4, and 1,5-diazabicyclo [4.3.0] -5-nonene in which m is 2. The substituents R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Preferably they are a C1-C20 alkyl group or a hydrogen atom, More preferably, they are a C1-C10 alkyl group or a hydrogen atom, Most preferably, they are a C1-C5 alkyl group or a hydrogen atom.
X ⁻ represents an anion. Specifically, halide ions, hydroxide ions, carbonate ions, bicarbonate ions, aliphatic and aromatic carboxy ions, aliphatic and aromatic sulfoxy ions, and their halides, hexafluoride Examples include antimonate ions (SbF ₆ ⁻ ) and phosphorus hexafluoride ions (PF ₆ ⁻ ). C ^* represents the carbon at the substitution site.

The compound (A2) represented by the general formula (2) will be described. (A2) of the present invention is a compound having an anthraquinone skeleton, and is an example of a compound having a maximum absorption wavelength in the vicinity of i-line (365 nm). The substituents R _{1 to} R ₈ are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc. For example, a hydrogen atom, a halogen atom, an alkoxy group (carbon number) 1-20), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1-20 carbon atoms), acyl group (1-20 carbon atoms), amino group, cyano group, alkyl group (1-20 carbon atoms) ), A functional group selected from the group consisting of a phenyl group and a naphthyl group.
However, any _{one of} the substituents R _{1 to} R ₈ is a substituent represented by the general formula (4).

Preferred examples of the substituent include a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, a phenyl group, and carbon. Examples thereof include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and an acyl group having 1 to 15 carbon atoms. Particularly preferred are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The alkyl moiety may be linear, branched or cyclic.

Specific examples of the substituent include the compounds described in the description of the compound (A1).

The compound (A3) represented by the general formula (3) will be described. (A3) of the present invention is a compound having a coumarin skeleton, and is an example of a compound having a maximum absorption wavelength in the vicinity of i-line (365 nm). Substituents R _{1 to} R ₆ are modified in consideration of absorption wavelength adjustment, sensitivity adjustment, thermal stability, reactivity, decomposability, etc., for example, hydrogen atom, halogen atom, alkoxy group (carbon number 1-20), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1-20 carbon atoms), acyl group (1-20 carbon atoms), amino group, cyano group, alkyl group (1-20 carbon atoms) ), A functional group selected from the group consisting of a phenyl group and a naphthyl group.
However, any _{one of} the substituents R _{1 to} R ₆ is a substituent represented by the general formula (4).

Preferred examples of the substituent include a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, a phenyl group, and carbon. Examples thereof include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and an acyl group having 1 to 15 carbon atoms. Particularly preferred are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The alkyl moiety may be linear, branched or cyclic.

Specific examples of the substituent include the compounds described in the description of the compound (A1).

Next, the polyimide precursor (B) contained in the photosensitive resin composition of the present invention will be described. (B) represents a compound that is converted to a polyimide by a base catalyst.

A polyamic acid is mentioned as (B) used for this invention. As described in J. Polymer Sci., A-1, 3, pp 1373 (1965), polyamic acid is an industrial process in which an equimolar amount of tetracarboxylic dianhydride and diamine are melt polycondensed in a polar solvent. This is an excellent synthesis method. Tetracarboxylic dianhydrides necessary for the synthesis of polyamic acid include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″. -P-terphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropanetetracarboxylic dianhydride 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propanetetracarboxylic dianhydride, 2,2-bis (4- (3,4-dicarboxyl) Nyl)) hexafluoropropanetetracarboxylic dianhydride, 2,2-bis (4- (3,4-dicarboxyphenyl)) propanetetracarboxylic dianhydride, 2,2-bis (p- (3 4-dicarboxyphenyl) phenyloxyphenyl) propanoic dianhydride, and one or more of these can be used

Examples of the diamine that reacts with the tetracarboxylic dianhydride include tetramethyl-1,4-phenylenediamine, hexamethylenediamine, tetraethyl-1,4-phenylenediamine, tetrapropyl-1,4-phenylenediamine, and trimethyl-1. , 4-phenylenediamine, triethyl-1,4-phenylenediamine, tripropyl-1,4-phenylenediamine, 3,3 ', 5'-trimethyl-4,4'-diaminobiphenyl, 3,3', 5 ' -Triethyl-4,4'-diaminobiphenyl, 3,3 ', 5'-tripropyl-4,4'-diaminobiphenyl, o-tolidine, p-phenylenediamine, 2,4-diaminodiphenyl ether, 4,4' -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'- Aminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4 "-diaminoterphenyl, 4,4" -diaminodicyclohexylmethane, 1,5-diaminonaphthalene, 4,4'-bis (p-aminophenoxy) Biphenyl, 4,4′-bis (m-aminophenoxy) diphenylsulfone, 2,2-bis (4- (p-aminophenoxy) phenyl) propane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,7-diaminofluorene, acetoguanamine, 3,3'-dimethoxybenzidine, m-phenylenediamine, 2,6-diaminoanthraquinone, 2,6-aminotoluene, 2,5-diaminopyridine, 2,6-diaminopyridine 2,5-diaminotoluene, 2,3-diaminopyridine, 3,4- Aminopyridine, 4,4'-diaminobenzophenone, 4,4'-bis (p-aminophenoxy) diphenylsulfone, benzoguanamine, 2,7-diaminonaphthalene, 3,4-diaminotoluene, m-xylenediamine, p-xylene Diamine, 4,4'-dithiodianiline, o-phenylenediamine, 4,4'-methylenebis (2-methylcyclohexylamine), 2,2-bis (4- (p, p'-aminobiphenyloxy) phenyl) Well-known things, such as a propane and p-xylenediamine, are mentioned.

Solvents used for polyamic acid synthesis include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, di- Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran, etc., alone However, you may mix and use.

Moreover, as a polyamic acid, you may use what is marketed.

If necessary, the photosensitive resin composition in the present invention may contain a solvent, a sensitizer, an adhesion promoter, and the like.

As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran, etc. May be. The solvent is preferably added so that the solid content concentration of the photosensitive resin composition is 1 to 100% by weight, more preferably 5 to 80% by weight, and particularly preferably 10 to 60% by weight.

Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive resin composition.

Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea Examples thereof include propyltriethoxysilane, tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. The content of the adhesion-imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive resin composition.

In the method of forming a pattern using the photosensitive resin composition of the present invention, the composition is first applied to a suitable support such as a silicon wafer, a ceramic, an aluminum substrate and the like. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after prebaking at 60 to 120 ° C. and drying the coating film, a desired pattern shape can be irradiated with radiation and actinic radiation. X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used as radiation and actinic rays, but i rays are preferable from the viewpoint of energy efficiency. Next, it is preferable to heat at 100-200 degreeC, and to promote imidation, while diffusing the basic substance which generate | occur | produced in the irradiation part surface layer part to the bottom part. Next, a pattern can be obtained by developing and dissolving and removing the unexposed portions.

Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and di-n-propylamine. Secondary amines such as, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. An alkaline aqueous solution and an aqueous solution to which an appropriate amount of a water-soluble organic solvent or a surfactant is added can be preferably used.

As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible. Next, the pattern formed by development can be rinsed. Distilled water can be used as the rinse liquid. Next, heat treatment can be performed to obtain a final pattern with high heat resistance. The heating temperature is generally 150 to 450 ° C.

The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, surface protective films and interlayer insulating films in semiconductor devices and interlayers in multilayer wiring boards are used. It can be used for forming an insulating film or the like. It can also be used for color filter protective films, organic EL insulating films, liquid crystal alignment films, optical lens protective films, and optical circuit materials for which photosensitive polyimide is required.

[Example]
EXAMPLES Hereinafter, although an Example and a manufacture example demonstrate this invention concretely, this invention is not limited to these. Hereinafter, parts represent parts by weight.

[Production of photobase generator (A)]
<Production Example 1>
4-Bromomethylbenzophenone (manufactured by Aldrich) and 7.33 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU, San Apro Co., Ltd.) 4.33 ml were added to acetonitrile (Wako Pure Chemical Industries, Ltd.) Manufactured) dissolved in 30 ml. While the liquid temperature was controlled at 25 ° C., the mixture was stirred for 24 hours. Thereafter, acetonitrile was removed by an evaporator. The obtained solid was washed with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.) and then recrystallized in acetonitrile to obtain a photobase generator (A1-1).

<Production Example 2>
4-Bromomethylbenzophenone (Aldrich) 7.76 g and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN, San Apro) 3.53 ml acetonitrile (Wako Pure Chemical Industries, Ltd.) )) Dissolved in 30 ml. While the liquid temperature was controlled at 25 ° C., the mixture was stirred for 24 hours. Thereafter, acetonitrile was removed by an evaporator. The obtained solid was washed with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and then recrystallized in acetonitrile. 3.80 g of the obtained solid was dissolved in 50 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and mixed with 3.49 g of sodium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 20 ml of methanol. did. The liquid temperature was kept at 25 ° C. and stirred for 3 hours. Thereafter, the precipitate was removed by filtration, and then methanol was removed by an evaporator. The photobase generator (A1-2) was obtained by washing with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.).

<Production Example 3>
8.49 g of 2-bromomethylanthraquinone (manufactured by Aldrich) and 4.33 ml of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU, manufactured by San Apro Co., Ltd.) acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) ) Dissolved in 30 ml. While the liquid temperature was controlled at 25 ° C., the mixture was stirred for 24 hours. Thereafter, acetonitrile was removed by an evaporator. The obtained solid was washed with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and then recrystallized in acetonitrile. 4.32 g of the obtained solid was dissolved in 50 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and mixed with 2.27 g of silver benzoate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 20 ml of methanol. . The liquid temperature was kept at 25 ° C. and stirred for 3 hours. Thereafter, the precipitate was removed by filtration, and then methanol was removed by an evaporator. A photobase generator (A2-1) was obtained by washing with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.).

<Production Example 4>
8.49 g of 2-bromomethylanthraquinone (manufactured by Aldrich) and 3.53 ml of 1,5-diazabicyclo [4.3.0] nonene-5 (DBN, manufactured by San Apro Co., Ltd.) acetonitrile (Wako Pure Chemical Industries, Ltd.) Manufactured) dissolved in 30 ml. While the liquid temperature was controlled at 25 ° C., the mixture was stirred for 24 hours. Thereafter, acetonitrile was removed by an evaporator. The obtained solid was washed with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and then recrystallized in acetonitrile. 4.05 g of the obtained solid was dissolved in 50 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), and 2.85 g of silver p-toluenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 20 ml of methanol. Mixed with. The liquid temperature was kept at 25 ° C. and stirred for 3 hours. Thereafter, the precipitate was removed by filtration, and then methanol was removed by an evaporator. A photobase generator (A2-2) was obtained by washing with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.).

<Production Example 5>
8.43 g of 4-bromomethyl-6,7-dimethoxycoumarin (manufactured by Aldrich) and 4.33 ml of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU, San Apro Co., Ltd.) acetonitrile (Wako Pure) The product was dissolved in 30 ml of Yakuhin Kogyo Co., Ltd. While the liquid temperature was controlled at 25 ° C., the mixture was stirred for 24 hours. Thereafter, acetonitrile was removed by an evaporator. The obtained solid was washed with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and then recrystallized in acetonitrile to obtain a photobase generator (A3-1).

<Production Example 6>
8.43 g of 4-bromomethyl-6,7-dimethoxycoumarin (manufactured by Aldrich) and 3.53 ml of 1,5-diazabicyclo [4.3.0] nonene-5 (DBN, manufactured by San Apro Co., Ltd.) in acetonitrile (Wako Pure) The product was dissolved in 30 ml of Yakuhin Kogyo Co., Ltd. While the liquid temperature was controlled at 25 ° C., the mixture was stirred for 24 hours. Thereafter, acetonitrile was removed by an evaporator. The obtained solid was washed with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and then recrystallized in acetonitrile. 4.03 g of the obtained solid was dissolved in 50 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and mixed with 3.49 g of sodium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 20 ml of methanol. did. The liquid temperature was kept at 25 ° C. and stirred for 3 hours. Thereafter, the precipitate was removed by filtration, and then methanol was removed by an evaporator. A photobase generator (A3-2) was obtained by washing with normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.).

[Production of photobase generator used in comparative example]
<Comparative Production Example 1>
As a photobase generator, {[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine (abbreviated as DNCDP) was synthesized by the method described in Non-Patent Document 1, Recrystallization from n-pentane and benzene gave a photobase generator (H-1). The obtained DNCDP had a yield of 65% and a melting point of 132.8 ° C., and the elemental analysis results were C; 58.12, H; 6.90, N; 7.94, O; . DNCDP is a compound that generates a secondary amine when irradiated with actinic rays.

<Comparative Production Example 2>
A photobase generator was synthesized in the same manner as in Production Example 1 of Patent Document 4. That is, 5 ml of distilled water in which 1.57 g (10 mmol) of N-phenylglycine and 400 mg of sodium hydroxide are dissolved is placed in a 50 mL (milliliter) flask and stirred at room temperature. Thereto, 10 mg of hydroquinone and 5 ml of methanol are added and completely dissolved, and then 1.42 g (10 mmol) of glycidyl methacrylate is gradually added dropwise. After stirring for 2 hours after completion of the dropwise addition, 1N hydrochloric acid was added to neutralize and a white precipitate was deposited. The precipitate was dried under reduced pressure to obtain 2.9 g of a photobase generator (H-2).

<Comparative Production Example 3>
A photobase generator was synthesized in the same manner as in Production Example 2 of Patent Document 4. That is, 1.19 g (1 mmol) of 4-vinylaniline, 1.52 g (1.1 mmol) of potassium carbonate, and 20 ml of dehydrated dimethylformamide are placed in a 100 ml flask and stirred. While the reaction vessel is cooled in an ice bath, 1.84 g (1.1 mmol) of ethyl bromoacetate is gradually added dropwise. After 24 hours, it was poured into 1 L of ice water, and the deposited precipitate was dried under reduced pressure to obtain 1.65 g of 4-vinylated product of N-phenylglycine ethyl ester. 1 g of the compound was dissolved in 3 ml of methanol, a lithium hydroxide saturated methanol solution was added dropwise while monitoring the progress of the reaction by thin layer chromatography, and the addition was terminated when the spot of the raw material disappeared, and the reaction The solution was neutralized with 1N hydrochloric acid and then poured into distilled water. The deposited precipitate was collected and dried under reduced pressure to obtain 420 mg of a photobase generator (H-3).

[Production of photosensitive resin composition]
Examples 1-6
3 parts of each of the photobase generators (A1-1 to A3-2) was mixed with 100 parts of an N-methyl-2-pyrrolidone solution of polyamic acid (Aldrich, solid content concentration 15% by weight) to prepare a photosensitive resin composition Q. -1 to Q-6 were produced.

[Production of comparative photosensitive resin composition]
Comparative Examples 1-3
3 parts of each of the comparative photobase generators (H-1 to H-3) are mixed with 100 parts of an N-methyl-2-pyrrolidone solution of polyamic acid (manufactured by Aldrich, solid content concentration: 15% by weight) to form a photosensitive resin composition. Q′-1 to Q′-3 were produced.

[Evaluation of curing temperature]
The curing temperature was evaluated by the remaining film rate as follows.

[Evaluation of remaining film ratio]
The photosensitive resin compositions Q-1 to Q-6 and the comparative photosensitive resin compositions Q′-1 to Q′-3 are spin-coated on a silicon substrate so as to have a final film thickness of 10 μm, and then heated to 100 ° C. Dry on a conditioned hotplate for 15 minutes.
Half of the dried silicon substrate was shielded with a mask, and then exposed with an i-line (365 nm) exposure device at an exposure amount of 1000 mJ / cm. The heating temperature after exposure was changed from 1700C to 250C in 10C increments. The heating time was 15 minutes. After heating, development was performed by immersing the silicon substrate in a 2% NaOH aqueous solution. The development time was the time until the light-shielded part (unexposed part) was completely dissolved.
After completion of development, washing was performed, and the remaining film ratio was calculated from the film thickness before exposure and the film thickness after development in the exposed portion. The results are shown in Table 1.

From Table 1, the photosensitive resin compositions Q-1 to Q-6 of the present invention are all good at a heating temperature of 200 ° C. and a residual film ratio of 90% or more, and the photosensitive resin composition Q′- of the comparative example. 1 to Q′-3 were found to have a remaining film ratio of 70% or less even at a heating temperature of 250 ° C.

[Evaluation of pattern formation ability]
When this photosensitive resin composition is applied to a semiconductor protective film and a printed circuit board protective film, it is essential that a pattern can be formed. The pattern forming ability was evaluated as follows.

On a hot plate whose temperature is adjusted to 100 ° C. after spin coating the photosensitive resin compositions Q-1 to Q-9 and Q′-1 to Q′-3 to a finished film thickness of 3 μm on a silicon substrate For 15 minutes.
It exposed with the exposure amount of 1000 mJ / cm with the i line | wire (365 nm) exposure machine using the photomask which can evaluate a line & space (L / S). After the exposure, it was heated at 150 ° C. for 5 minutes. Thereafter, development was performed using a 2% NaOH aqueous solution. After development, after washing with water, a pattern was obtained by heating at 200 ° C. for 15 minutes. Table 2 shows the minimum L / S obtained.

From Table 2, photosensitive resin compositions Q-1 to Q-6 were all good with a minimum L / S of 5 μm. Q′-1 to Q′-3 had a minimum L / S of 15 μm or more. In addition, there were some defects in the pattern.

As seen in this example, it can be seen that a polyimide can be obtained by a low temperature process by using the photosensitive resin composition of the present invention. Therefore, it is particularly useful for a protective film of a semiconductor component that cannot withstand a high temperature process and a printed circuit board.

The photosensitive resin composition of the present invention is suitably used for a semiconductor protective film and a printed circuit board protective film in which a low-temperature curing process is useful.

Claims (5)

A compound (A1) represented by the general formula (1), a compound (A2) represented by the general formula (2), and a compound (A3) represented by the general formula (3). A photosensitive resin composition comprising a photobase generator (A) that generates a base upon irradiation with actinic rays and a polyimide precursor (B).
(Substituents R _{1 to} R ₁₀ are hydrogen atom, halogen atom, alkoxy group (1 to 20 carbon atoms), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1 to 20 carbon atoms), acyl group (carbon Selected from the group consisting of an amino group, a cyano group, an alkyl group (1 to 20 carbon atoms), a phenyl group, and a naphthyl group, provided that any _{one of} substituents R _{1 to} R ₁₀ is It is a substituent represented by the general formula (4).)
(Substituents R _{1 to} R ₈ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl group (carbon Selected from the group consisting of an amino group, a cyano group, an alkyl group (1 to 20 carbon atoms), a phenyl group, and a naphthyl group, provided that any _{one of} substituents R _{1 to} R ₈ is It is a substituent represented by General formula (4).
(Substituents R _{1 to} R ₆ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl group (carbon Selected from the group consisting of an amino group, a cyano group, an alkyl group (having 1 to 20 carbon atoms), a phenyl group, and a naphthyl group, provided that at least one of the substituents R _{1 to} R ₆ is general. It is a substituent represented by Formula (4).
(Substituents R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. M represents an integer of 2 to 4. X ⁻ represents an anion. C ^* represents carbon at a substituted site. .) The photosensitive resin composition according to claim 1, wherein m is 2 or 4 in the general formula (4). The photosensitive resin composition according to claim 1, wherein the polyimide precursor (B) is a polyamic acid. The semiconductor protective film formed using the photosensitive resin composition of any one of Claims 1-3. The printed circuit board protective film formed using the photosensitive resin composition of any one of Claims 1-3.