JP3165024B2 - Photosensitive resin composition and method for forming patterned polyimide film using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition useful for forming a protective film such as a protective insulating film for a semiconductor device, an alignment film for a liquid crystal display device, and an insulating film for a multilayer printed circuit board. The present invention relates to a method for forming a patterned polyimide film to be used.

[0002]

2. Description of the Related Art Conventionally, as a heat-resistant photosensitive material, for example,
Material consisting of polyamic acid and dichromate
No. 49-17374 (corresponding to U.S. Pat. No. 3,623,870, British Patent No. 1316976 and Canadian Patent No. 918484), a material comprising a carboxyl group of a polyamic acid having a photosensitive group introduced by an ester bond [ Kaisho 49
-115541, JP-A-55-45746 (U.S. Pat.
No. 3,957,512, corresponding to British Patent No. 1467226)], a material family comprising a polyamic acid and an amine compound having a photosensitive group [JP-A-54-145794 (US Pat.
243,743)], and a material comprising a photosensitive group introduced into a carboxyl group of a polyamic acid through a silyl ester bond (JP-A-62-275129).

However, these materials use an organic solvent as a developing solution at the time of pattern formation, and the use of the organic solvent has a problem such as an influence on the health of workers and a waste liquid treatment.

[0004]

Therefore, in order to solve the above-mentioned problems, as a material which can be developed with an aqueous liquid,
For example, a material comprising a photosensitive group introduced into a carboxyl group of a polyamic acid through an amide bond [Japanese Patent Laid-Open No.
No. 100143, JP-A-2-157845 (U.S. Pat.
515,887, 4,587,204, and UK Patent No. 2145728)], a positive photosensitive resin composition (Polymer Engine) comprising a naphthoquinonediazidesulfonic acid ester mixed with a phenol group-containing polyimide resin.
ering AndScience, July 1989, Vol. 29, 954).

However, these materials have problems that a long time is required for development and that the sensitivity is not sufficient particularly when forming a thick film.

[0006] Accordingly, an object of the present invention is to develop an aqueous solution in a short time and to have sufficient sensitivity.
It is an object of the present invention to provide a photosensitive resin composition capable of easily forming a patterned polyimide film and a method for forming a patterned heat-resistant polyimide film using the composition.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, when a specific polyimide precursor and a photosensitizer are blended, development with an alkaline aqueous solution is possible. A negative-type photosensitive polyimide resin composition can be obtained. Such a composition has little contamination with ionic impurities during production and has good sensitivity to light irradiation and can easily form a pattern. It has been found that, when such a composition is cured, a polyimide film having excellent heat resistance and excellent electrical and mechanical properties is formed, and the present invention has been completed.

The present invention provides (A) the following general formula (1):

Embedded image [Wherein, X is a tetravalent organic group having an aromatic ring;
Is a divalent organic group having an aromatic ring or a divalent organic group having a siloxane bond. The two Zs may be the same or different, and are a hydrogen atom or the following general formula (2):

[0009]

Embedded image (Where R is a hydrogen atom or a methyl group.) 1 containing an acryloxy or methacryloxy group
And two Ws may be the same or different, and may be a hydroxyl group or a general formula (3): —NH—CH ₂ CH ₂ OCO—C (R ′) = CH ₂ (3) (where, R 'is a hydrogen atom or a methyl group.) Is an amino group containing an acryloxy group or a methacryloxy group. The polyimide precursor comprising the structural unit represented by the formula, wherein the proportion of the monovalent organic group represented by the general formula (2) is at least 30 of all Z contained in the polyimide precursor Mol%, and the proportion of the amino group represented by the general formula (3) is 10 to 50 mol% in all W contained in the polyimide precursor; and (B) a sensitizer, Provided is a photosensitive resin composition containing a photopolymerization initiator or a combination thereof.

Further, the present invention provides a method for applying a solution of the above-mentioned photosensitive resin composition to a substrate, drying the film to form a film, exposing the film, developing the exposed film using a developer, A method for forming a patterned polyimide film having a step of curing an obtained pattern, wherein an alkaline aqueous solution is used as the developer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) polyimide precursor polyimide precursor which is an active ingredient of the composition of the present invention (A)
Is composed of the structural unit represented by the general formula (1). X in the general formula (1) is a tetravalent organic group having an aromatic ring. The plurality of Xs contained in the polyimide precursor (A) are
They may be the same or different. As a typical example of X,

[0012]

Embedded image And the like, but are not limited thereto.
Preferred of these Xs are as follows.

[0013]

Embedded image

Y in the above formula (1) is a divalent organic group having an aromatic ring or a divalent organic group having a siloxane bond. Of course, Y may be a divalent organic group having an aromatic ring and a siloxane bond. A plurality of Ys contained in the polyimide precursor (A) may be the same or different.

As the divalent organic group Y having an aromatic ring, specifically, for example, the following general formula (4):

Embedded image

[In the formula, a plurality of R ² may be the same or different, and may be -H, -Cl, -CONH ₂ or an alkyl group having 1 to 3 carbon atoms (eg, -CH ₃ , -CH ₂ CH ₃ , −CH ₂ CH ₂ CH
_3, is -CH (CH _{3) 2,} etc.). A group represented by

The following general formula (5):

Embedded image

Wherein R ¹ is a single bond, —O—, ─SO ₂
-, - S- or a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms _{(e.g., -CH 2 -, - C (} CH 3) 2 -,
-CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ )
-, -, and the _{like) - C (CF 3) 2} . A plurality of R ² may be the same or different and are as described above. A group represented by

The following general formula (6):

Embedded image

[Wherein, a plurality of R ¹ may be the same or different and are as described above, and a plurality of R ² may be the same or different and are as described above. A group represented by

The following general formula (7):

Embedded image

[Wherein, R ¹ may be the same or different and is as described above, and a plurality of R ² may be the same or different and is as described above. And the like represented by
As the divalent organic group Y having a siloxane bond, for example,

The following general formula (8):

Embedded image

[In the formula, a plurality of R ³ may be the same or different, and an alkylene group having 3 or 4 carbon atoms (for example,-
CH ₂ CH ₂ CH _2- , --CH ₂ CH ₂ CH ₂ CH _2-, etc.), phenylene group, or

Formula:

Embedded image Is a group represented by A plurality of R ^{4 s} may be the same or different and have an alkyl group having 1 to 3 carbon atoms (for example, -C
H ₃ , —CH ₂ CH ₂ CH ₃ etc.), and m is an integer of 1 to 40. A group having a siloxane bond represented by the following formula:

The above-mentioned divalent organic group Y may be contained alone, or may be contained in the above-mentioned general formulas (4), (5), (6) and (7).
And a combination of at least two groups represented by (8), for example, at least one group represented by general formulas (4), (5), (6) and (7) and a group represented by general formula (8) May be included in combination with the group. Preferred among these divalent organic groups Y are those represented by the general formulas (5), (7) and (8).
Is a group represented by

Two Z's in the above general formula (1) may be the same or different, and may be a hydrogen atom or the following general formula (2):

Embedded image

(Where R is a hydrogen atom or a methyl group) is a monovalent organic group containing an acryloxy group or a methacryloxy group. The polyimide precursor
In (A), the proportion of the monovalent organic group represented by the general formula (2) is at least 30 mol%, preferably 30 to 80 mol, of all Z contained in the precursor. %. The ratio of the monovalent organic group represented by the general formula (2) is 3
When the amount is less than 0 mol%, sufficient sensitivity cannot be obtained when the photosensitive composition is used. In the general formula (1), two Ws may be the same or different, and may be a hydroxyl group or a general formula (3): —NH—CH ₂ CH ₂ OCO—C (R ′) = CH ₂ (3) (where R 'Is a hydrogen atom or a methyl group.) Is an amino group containing an acryloxy group or a methacryloxy group. The substituted amino group of the general formula (3) is
In the polyimide precursor (A), 10% of all W
５０50 mol%, preferably 20-40 mol%. If the substituted amino group is less than 10 mol%, the solubility in an aqueous alkali solution used as a developer is too high to control the development time, and if it exceeds 50 mol%, the unexposed portion is used as a developer after exposure. There is a problem that it does not dissolve in an alkaline aqueous solution.

The average molecular weight (for example, weight average molecular weight) of the polyimide precursor (A) is 10,000 or more, more preferably 20,000 to 200,000. When the average molecular weight is less than 10,000, a cured film obtained by curing the composition does not have sufficient strength. On the other hand, when the average molecular weight exceeds 200,000, the viscosity of the composition solution is too high, resulting in poor workability and unsuitability for use.

The polyimide precursor (A) has, for example, the following general formula (9):

Embedded image (Wherein X is as defined above), and a tetracarboxylic dianhydride represented by the formula:

The following general formula (10):

Embedded image

(Wherein Y and Z are as defined above) in a suitable solvent, usually at 0 to 40 ° C., to give a compound of the general formula (11):

Embedded image (Where X, Y and Z are as defined above), and then the product is converted to a compound of the general formula (12): CH ₂ ＣC (R ′)- ₂ represented by COOCH ₂ CH ₂ NCO (12) (where R ′ is as defined above)
-Made by reacting with isocyanatoethyl (meth) acrylate. The production of the polyimide precursor (A) is not limited to such a production method.

In the above process, the number of moles of the tetracarboxylic dianhydride and the number of moles of the diamine compound are:
Almost equimolar.

The diamine compound is represented by the following general formula (13):

Embedded image (Wherein, Y is as defined above),

The following general formula (14):

Embedded image Wherein Y is as described above, and Z ′ is
It is a monovalent organic group represented by (2). A), and

The following general formula (15):

Embedded image (Wherein Y and Z ′ are as defined above), and in all Z (ie, the sum of Z ′ and the hydrogen atom bonded to the nitrogen atom), at least 30 mol%
Must be used in combination with the diamine compounds represented by the above general formulas (10) to (12) at a ratio such that

As the solvent used in the reaction between the tetracarboxylic dianhydride and the diamine compound, any solvent can be used. Specifically, for example, N-methyl-2- Pyrrolidone, dimethylacetamide, dimethylformamide, hexamethylphosphorylamide, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, Organic solvents such as cyclohexanone, γ-butyrolactone, butyl cellosolve acetate, toluene, xylene, anisole, methylanisole, and ethylphenyl ether; It is. These can be used alone or in combination of two or more.

The tetracarboxylic dianhydride represented by the general formula (9) includes, for example, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis
[4- (3,4-dicarboxyphenoxy) phenyl] propanoic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) perfluoropropanoic dianhydride, bis (3,4-dicarboxy) Phenyl) dimethylsilane dianhydride, 1,3-bis (3,4
-Dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride and the like;
It can be used in combinations of more than one species. Of these tetracarboxylic dianhydrides, preferred are pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) perfluoropropanoic acid dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride It is.

Examples of the diamine compound represented by the general formula (13) include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamine.
Diaminodiphenyl ether, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 1,4-bis (3-aminophenoxy) benzene, 4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthioether) ) Benzene, 1,4-bis (m-aminophenylthioether) benzene, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-
4- (4-aminophenoxy) phenyl] propane, 1,1-bis
[4- (4-aminophenoxy) phenyl] ethane, 1,1-bis
[3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl] -4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro -4- (4-
Aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis
Aromatic diamine compounds such as [4- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane;

For example, the following formula:

Embedded image An aromatic diamine compound having an amide group represented by

For example, the following formula:

Embedded image Examples thereof include, but are not limited to, diaminoorganosiloxane compounds represented by Also,
These can be used alone or in combination of two or more.

Among the diamine compounds represented by the general formula (13), preferred are as follows.

Embedded image

Further, the acryloxy group and / or methacryloxy group-containing diamine compound represented by the above general formulas (14) and (15) is composed of a diamine compound represented by the above general formula (13), glycidyl acrylate and / or glycidyl acrylate. Alternatively, it can be easily produced by reacting with glycidyl methacrylate usually at 60 to 120 ° C. Examples of the diamine compound of the general formula (13) used herein are as described above.
Further, the reaction between the compound of the general formula (11) and 2-isocyanatoethyl (meth) acrylate proceeds only by mixing at room temperature in an organic solvent. As the organic solvent, those exemplified above can be used.

(B) a sensitizer, a photopolymerization initiator, or a
Combination The photosensitive resin composition of the present invention contains a sensitizer and / or a photopolymerization initiator (B) as an active ingredient.

Examples of sensitizers include benzophenone, acetophenone, anthrone, phenanthrene, nitrofluorene, nitroacenaphthene, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, chloro Thioxanthone, benzanthraquinone, 2,6-bis- (4-diethylaminobenzal) -cyclohexanone, 2,6-bis- (4-diethylaminobenzal) -4-methyl-cyclohexanone, 4,4'-bis- (diethylamino ) Chalcone, 2,4-diethylthioxanthone, N-phenyl-diethanolamine, diethylaminoethyl methacrylate, coumarin compounds and the like, but are not limited thereto. The sensitizers can be used alone or in combination of two or more. Of the above sensitizers, preferred are 2,6-bis (4-diethylaminobenzal) cyclohexanone,
Diethylthioxanthone, diethylaminoethyl methacrylate and coumarin compounds.

Examples of the photopolymerization initiator include benzyl, benzoin isopropyl ether, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, N-phenylglycine, 3-phenyl-5
-Examples include isoxazolone, camphorquinone, biimidazoles such as 2,2-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, It is not limited to these. Further, the photopolymerization initiator can be used alone or in combination of two or more. Among the above photopolymerization initiators, preferred are N-phenylglycine, 3-phenyl-5-isoxazolone and biimidazoles.

The sensitizer and the photopolymerization initiator can be used in combination.

The compounding amount of the sensitizer and / or the photopolymerization initiator is arbitrary, but generally, the polyimide precursor (A)
It is 0.1 to 20% by weight of the component, preferably 0.5 to 10% by weight.

Photosensitive resin composition The photosensitive resin composition of the present invention comprises a solution prepared by dissolving the above-mentioned polyimide precursor (A) and a sensitizer and / or a photopolymerization initiator (B) in a suitable organic solvent. Stored and used as.

As the above-mentioned organic solvent, for example, the organic solvents exemplified as those for producing the polyimide precursor (A) are preferably used, and these organic solvents may be used alone or in combination of two or more. I do. The amount of the organic solvent used is preferably such that the concentration of the polyimide precursor (A) is 5 to 50% by weight.

The solution obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent is applied to a substrate such as a silicon wafer, a metal plate, a glass plate, a ceramic substrate or the like by a known method such as spin coating, dipping, or printing. After the formation of the coating film by drying, a polyimide protective film having excellent properties such as heat resistance is formed through various steps of exposure, development with an aqueous alkali solution, and curing.

The coating film is formed by drying, for example, a dryer,
Pre-baking can be performed at a temperature of 30 to 180 ° C. for several minutes to several hours using a heating means such as a hot plate to remove most of the organic solvent in the coating film.

Exposure is performed by placing a photomask on the film formed above and irradiating light such as visible light and ultraviolet light for several seconds to several minutes.

After exposure, a relief pattern can be obtained by dissolving and removing the unexposed portion with a developing solution. Here, since an alkaline aqueous solution is used as the developing solution, there is no effect on health and no problem of waste liquid treatment. The development time may be generally about 10 seconds to 3 minutes. Examples of the alkaline aqueous solution include an aqueous solution of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; for example, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; For example, an aqueous solution of an organic amine such as methyldiethanolamine or triethanolamine, preferably an aqueous solution of tetramethylammonium hydroxide is exemplified. The concentration of the alkaline aqueous solution is preferably 0.01 to 30% by weight.

Further, the resin of the relief pattern formed by the development is heated at a temperature of usually 200 to 500 ° C., preferably 300 to 400 ° C. for several tens minutes to several hours by a heating means such as a drier or an electric furnace. As a result, a patterned polyimide film can be formed.

As described above, the photosensitive resin composition of the present invention can easily form a pattern, and the resin film formed by curing the resin composition has excellent heat resistance, mechanical properties, and electrical properties. It can be widely used as a protective film for electronic parts. Specifically, for example, a diode, a transistor, an I.D. C. , L .; S. I. Junction coat film, passivation film, buffer coat film, L. S. I. It is preferably used as an α-ray shielding film, an interlayer insulating film for multilayer wiring, a conformal coat for a printed circuit board, an alignment film for a liquid crystal display element, and a protective film for electronic components such as an ion implantation mask.

[0057]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Solution of Polyimide Precursor After replacing the inside of a flask equipped with a stirrer and a thermometer with nitrogen gas, 40.04 g of 4,4'-diaminodiphenyl ether and 34.04 g of glycidyl methacrylate were placed in the flask. g and
355 g of N-methyl-2-pyrrolidone was charged and stirred for 15 hours while maintaining the temperature at 90 ° C. After the obtained reaction solution was cooled, it was analyzed by gel permeation chromatography. As a result, glycidyl methacrylate as a raw material disappeared, and glycidyl methacrylate adduct and 4,2′-adduct of 4,4′-diaminodiphenyl ether were formed. Was.

To the above reaction solution, 58.0 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 1,3-bis (3,4-
8.52 g of (dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride were added with cooling so that the temperature of the solution did not exceed 30 ° C. After the addition was completed, the mixture was stirred at room temperature for 24 hours. Thereafter, 12.40 g of 2-isocyanatoethyl methacrylate was added to the reaction solution, and the mixture was further stirred for 24 hours. During that time, the evolution of carbon dioxide was observed. After completion of the stirring, the reaction solution was subjected to gel permeation chromatography. As a result, disappearance of 2-isocyanatoethyl methacrylate was confirmed.

Thus, the following equation:

Embedded image (Wherein Z ″ is the same or different and is a hydrogen atom, or the following formula:

Embedded image Wherein W ′ is the same or different and is a hydroxyl group or a 2-methacryloxyethylamino group), and a structural unit represented by the following formula:

Embedded image (Wherein, Z ″ and W ′ are as defined above), and the ratio of the methacryloxy group-containing group to the total Z ″ is 60 mol%, and the total W ′ The proportion of 2-methacryloxyethylamino groups in the total is 20 mol%
Solution of the polyimide precursor (viscosity at 25 ° C .:
2600 cP). The weight average molecular weight of this polyimide precursor was about 65000 (GPC, converted to polystyrene).

Preparation Example 2 Preparation of Solution of Polyimide Precursor After the inside of a flask equipped with a stirrer and a temperature system was replaced with nitrogen gas, 39.60 g of 4,4′-diaminodiphenylmethane and glycidyl methacrylate were placed in the flask. g and N-
300 g of methyl-2-pyrrolidone was charged and stirred for 20 hours while maintaining the temperature at 80 ° C. After the obtained reaction solution was cooled and analyzed by gel permeation chromatography, glycidyl methacrylate as a raw material disappeared, and glycidyl methacrylate adduct of 4,4'-diaminodiphenylmethane and a diadduct were formed. Was.

To the reaction solution, 29.42 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 42.60 g of tetramethyldisiloxane dianhydride were added with cooling so that the temperature of the solution did not exceed 30 ° C. After the addition was completed, the mixture was stirred at room temperature for 10 hours. Thereafter, 31.00 g of 2-isocyanatoethyl methacrylate was added to the reaction solution, and the mixture was further stirred for 24 hours. During that time, the generation of carbon dioxide was observed. After completion of the stirring, the reaction solution was subjected to gel permeation chromatography. As a result, disappearance of 2-isocyanatoethyl methacrylate was confirmed.

Thus, the following equation:

Embedded image (Wherein, Z ″ and W ′ are as defined above) and the following formula:

Embedded image (Wherein, Z ″ and W ′ are the same as described above), wherein the proportion of the methacryloxy-containing group in all Z ″ is 30 mol%, and 2% in all W ′
A solution of a polyimide precursor in which the proportion of methacryloxyethylamino groups is 50 mol% (viscosity at 25 ° C. 43
00cP). The weight average molecular weight of this polyimide precursor was about 45000 (GPC, converted to polystyrene).

Preparation Example 3 Preparation of Solution of Polyimide Precursor After replacing the inside of a flask equipped with a stirrer and a thermometer with nitrogen gas, 73.9 g of 2,2-bis (4-aminophenoxyphenyl) propane, glycidyl methacrylate 28.4g and N
-Methyl-2-pyrrolidone (500 g),
The mixture was stirred for 15 hours while maintaining the temperature at ° C. After cooling the obtained reaction solution, it was analyzed by gel permeation chromatography. As a result, glycidyl methacrylate as a raw material disappeared, and glycidyl methacrylate adduct of 2,2-bis (4-aminophenoxyphenyl) propane and 2 The formation of the adduct was confirmed.

First, 5.0 g of 1,3-bis (3-aminopropyl) 1,1,3,3-tetramethyldisiloxane was added to the reaction solution, and then 2,2-bis (3,4-dicarboxy) was added. 88.8 g of phenyl) perfluoropropanoic acid dianhydride was added at a solution temperature of 3
It was added while cooling so as not to exceed 0 ° C. After the addition was completed, the mixture was stirred at room temperature for 24 hours. Then, 2-
6.2 g of isocyanatoethyl methacrylate was added, and the mixture was further stirred for 24 hours. During that time, the evolution of carbon dioxide was observed. After completion of the stirring, the reaction solution was subjected to gel permeation chromatography. As a result, disappearance of 2-isocyanatoethyl methacrylate was confirmed.

Thus, the equation:

Embedded image And a structural unit represented by:

Embedded image Wherein Z ″ and W ′ are as defined above, and the methacryloxy-containing group in all Z ″ is 50 mol%, and the total methacryloxy in W ′ is 2-methacryloxy. A polyimide precursor solution (viscosity: 7000 cP (25 ° C.)) containing 10 mol% of ethylamino groups was obtained. The obtained resin has a weight average molecular weight of about 90,000 (GPC, polystyrene equivalent).
Met.

Preparation Example 4 Preparation of Solution of Polyimide Precursor for Comparison After the inside of a flask equipped with a stirrer and a thermometer was replaced with nitrogen gas, 40.04 g of 4,4'-diaminodiphenyl ether and methacryl were placed in the flask. Glycidyl acid 14.2 g, N-
355 g of methyl-2-pyrrolidone was charged, and the solution was stirred for 15 hours while maintaining the temperature of the solution at 90 ° C. After cooling the obtained reaction solution, it was analyzed by gel permeation chromatography. As a result, the raw material glycidyl methacrylate disappeared, and the monoadduct and diadduct of 4,4′-diaminodiphenyl ether and glycidyl methacrylate were removed. Had been generated.

To this reaction solution, 58.0 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 -Reaction temperature of the solution with 8.52 g of tetramethyldisiloxane dianhydride at 30 ° C
While cooling so as not to exceed. After the addition, the mixture was stirred at room temperature for 24 hours. Thereafter, 12.40 g of 2-isocyanatoethyl methacrylate was added to the reaction solution, and 24
Stirred for hours. During that time, the generation of carbon dioxide was observed,
After completion of the stirring, the reaction solution was subjected to gel permeation chromatography. The disappearance of 2-isocyanatoethyl methacrylate was observed, and the viscosity at 25 ° C. was 3800 cp.
To obtain a solution of the methacrylate group-containing polyimide precursor aimed at. In this precursor, the proportion of methacryloxy groups in all Z is 25%, and the proportion of methacryloxyethylamino groups in all W is 20%.
The weight average molecular weight of this polyimide precursor is about 45,000 (G
PC, polystyrene equivalent).

Preparation Example 5 Preparation of Solution of Comparative Polyimide Precursor After the inside of a flask equipped with a stirrer and a thermometer was replaced with nitrogen gas, 40.04 g of 4,4′-diaminodiphenyl ether and methacryl were placed in the flask. Glycidyl acid 28.4 g, N-
355 g of methyl-2-pyrrolidone was charged, and the solution was stirred for 15 hours while maintaining the temperature of the solution at 90 ° C. After cooling the obtained reaction solution, it was analyzed by gel permeation chromatography. As a result, the raw material glycidyl methacrylate disappeared, and the monoadduct and diadduct of 4,4′-diaminodiphenyl ether and glycidyl methacrylate were removed. Had been generated.

To this reaction solution, 58.0 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 -Reaction temperature of the solution with 8.52 g of tetramethyldisiloxane dianhydride at 30 ° C
While cooling so as not to exceed. After the addition, the mixture was stirred at room temperature for 24 hours. Thereafter, 3.1 g of 2-isocyanatoethyl methacrylate was added to the reaction solution, and the mixture was further stirred for 24 hours. In the meantime, the generation of carbon dioxide was observed, and after completion of stirring, when subjected to gel permeation chromatography, disappearance of 2-isocyanatoethyl methacrylate was observed, and the objective methacrylate group-containing substance having a viscosity of 2800 cp at 25 ° C. A solution of the polyimide precursor was obtained. In this precursor, the proportion of methacryloxy groups in all Z is 50%, and the proportion of methacryloxyethylamino groups in all W is 5%. The weight average molecular weight of this polyimide precursor was about 35,000 (GPC, converted to polystyrene).

Preparation Example 6 Preparation of Solution of Comparative Polyimide Precursor After replacing the inside of a flask equipped with a stirrer and a thermometer with nitrogen gas, 40.04 g of 4,4'-diaminodiphenyl ether and methacrylic acid were added to the flask. Glycidyl (22.72 g) and N-methyl-2-pyrrolidone (355 g) were charged, and the solution was stirred for 15 hours while maintaining the temperature at 90 ° C. After cooling the obtained reaction solution, it was analyzed by gel permeation chromatography. As a result, the raw material glycidyl methacrylate disappeared, and the monoadduct and diadduct of 4,4′-diaminodiphenyl ether and glycidyl methacrylate were removed. Had been generated.

To this reaction solution, 58.0 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 -Reaction temperature of the solution with 8.52 g of tetramethyldisiloxane dianhydride at 30 ° C
While cooling so as not to exceed. After the addition, the mixture was stirred at room temperature for 24 hours. Thereafter, 34.1 g of 2-isocyanatoethyl methacrylate was added to the reaction solution, and the mixture was further stirred for 24 hours. In the meantime, generation of carbon dioxide was observed, and after completion of stirring, when subjected to gel permeation chromatography, disappearance of 2-isocyanatoethyl methacrylate was observed, and the target methacrylate group-containing substance having a viscosity of 2100 cp at 25 ° C. A solution of the polyimide precursor was obtained. In this precursor, the proportion of methacryloxy groups in all Z is 40%, and the proportion of methacryloxyethylamino groups in all W is 55%. The weight average molecular weight of this polyimide precursor was about 30,000 (GPC, converted to polystyrene).

Examples 1 to 5 The solution of the polyimide precursor prepared above, or 1
The components (B) shown in Table 1 were added to 00 parts by weight in the amounts shown in Table 1 to prepare five types of photosensitive resin compositions (Examples 1 to 5).

Thereafter, each solution of each composition prepared in each Example was applied on a silicon wafer using a spin coater, and dried on a hot plate at 90 ° C. for 4 minutes to form a coating film. A photomask having a stripe pattern is brought into close contact with the obtained coating film,
Ultraviolet light from a W ultra-high pressure mercury lamp was applied for 60 seconds. Next, a 2.3% aqueous solution of tetramethylammonium hydroxide (TMAH) and a 0.5N K
Each of the OH aqueous solutions was used to develop the sample after the end of the ultraviolet irradiation. The development is carried out in the alkaline aqueous solution,
The test was performed by immersing the sample for 1 minute. After the development was completed, each sample was rinsed with dull water, the obtained line and space pattern shape was observed, and the minimum line width (resolution) was measured. Table 1 shows the results.
Shown in

Each of the obtained samples was placed in a dryer for 150 minutes.
At 0.5 ° C for 0.5 hour and then at 350 ° C for 1 hour to cure.
The adhesion between the cured coating film and the silicon wafer as the substrate was evaluated by a grid test. Table 1 shows the results.

The evaluation of the adhesion by a grid test was performed by setting 100 grids in a grid pattern at intervals of 1 mm on the cured coating film, and attaching the adhesive tape to peel off the grid. Indicated.

[0077]

[Table 1]

From the results shown in Table 1, the solutions of the resin compositions obtained in Examples 1 to 5 have good photosensitivity even for relatively thick films, can be easily developed with an aqueous alkali solution, and Gives a good pattern after development,
It is understood that it has excellent adhesiveness to a silicon wafer and is suitably used as a protective film for electronic components.

Comparative Examples 1 to 3 To the solution or 100 parts by weight of the comparative polyimide precursor prepared above, the component (B) shown in Table 2 was added in the amounts shown in Table 2 to obtain three kinds of Photosensitive resin compositions were prepared (Comparative Examples 1 to 3). In accordance with the methods described in Examples 1 to 5, films were prepared from the solutions of the above-prepared compositions and tested for developability and adhesion. Table 2 shows the results.

[0080]

[Table 2] (Note) c: 2,6-bis- (4-diethylaminobenzal) -4-methyl-cyclohexanone e: N-phenylglycine

[0081]

The photosensitive resin composition of the present invention has almost no ionic impurities at the time of its production, and its solution has excellent storage stability and is an alkali which does not cause health problems or waste liquid treatment problems. It is developed in an aqueous solution in a short time, and also has good sensitivity when forming a thick film,
Provides an easily patterned resin film. Furthermore, by heating and curing this patterned film,
A polyimide film having particularly excellent heat resistance, electrical and mechanical properties is obtained, and this film can be suitably used as a protective film for electronic parts.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-4226 (JP, A) JP-A-2-154261 (JP, A) JP-A-4-224823 (JP, A) JP-A 55- 45746 (JP, A) JP-A-55-9538 (JP, A) JP-A-6-258833 (JP, A) JP-A-59-68332 (JP, A) JP-A-54-89623 (JP, A) (58) Investigated field (Int.Cl. ⁷ , DB name) G03F 7/038 C08L 79/08 G02F 1/1337 525 H01L 21/027 H05K 3/28

Claims (2)

(57) [Claims] (A) The following general formula (1): [Wherein, X is a tetravalent organic group having an aromatic ring;
Is a divalent organic group having an aromatic ring or a divalent organic group having a siloxane bond, and two Z's may be the same or different, and represent a hydrogen atom or the following general formula (2): (Where R is a hydrogen atom or a methyl group.) 1 containing an acryloxy or methacryloxy group
And two Ws may be the same or different, and may be a hydroxyl group or a general formula (3): —NH—CH ₂ CH ₂ OCO—C (R ′) = CH ₂ (3) (where, R 'is a hydrogen atom or a methyl group), and is an amino group containing an acryloxy group or a methacryloxy group. Is a polyimide precursor having an average molecular weight of 10,000 or more, wherein the proportion of the monovalent organic group represented by the general formula (2) is all contained in the polyimide precursor. Is at least 30 mol% in Z, and the proportion of the amino group represented by the general formula (3) is 1% in all W contained in the polyimide precursor.
A photosensitive resin composition comprising 0 to 50 mol% and (B) a sensitizer, a photopolymerization initiator, or a combination thereof. 2. A solution of the photosensitive resin composition according to claim 1 is applied to a substrate, dried to form a film, the film is exposed, and the exposed film is developed using a developer. A method for forming a patterned polyimide film having a step of curing an obtained pattern, wherein an alkaline aqueous solution is used as the developer.