JP3407780B2 - Photosensitive resin composition and pattern forming method thereof - 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 for obtaining a pattern having excellent adhesion and high resolution, and a pattern forming method thereof.

[0002]

2. Description of the Related Art Conventionally, a polyimide having excellent heat resistance and excellent electrical insulation and mechanical strength has been used for a surface protective film, an interlayer insulating film, etc. of a semiconductor element. Recently, a technique for imparting photosensitivity to polyimide itself has been attracting attention in order to simplify the complicated process.

For example, the following formula

[Chemical 5] A polyimide precursor composition having a photosensitive group with an ester group having a structure as shown in (for example, Japanese Examined Patent Publication No. 55-41).
No. 422) and the like are known. All of these are dissolved in an appropriate organic solvent, applied in a varnish state, dried, irradiated with ultraviolet rays through a photomask, developed and rinsed to obtain a desired pattern, and further subjected to heat treatment to form a polyimide. It is a film.

The use of polyimide having photosensitivity not only has the effect of simplifying the pattern forming process, but it is also safe and excellent in pollution because it does not require the use of an etching solution which has a problem in the working environment. It is expected that the photosensitization of polyimide will become an even more important technology in the future. However, although various techniques for increasing the photosensitivity of the polyimide precursor to which such an ester group is added have been investigated (JP-A-6-342211, 7-5688, etc.), a finer high-resolution pattern can be formed. There was no consideration to get. Therefore, the resolution of a photosensitive resin composition obtained from a varnish obtained by dissolving a polyimide precursor having an ester group together with a photopolymerization initiator in a polar solvent has a resolution due to swelling of a developing solution, etc. It is worse than the negative resist of the system, and its improvement has been demanded. In particular, when such a photosensitive resin composition is coated on a substrate, exposed to light, and developed, an insoluble matter is deposited at the interface with the substrate, resulting in a significant decrease in resolution, which is a problem.

When a polyimide resin is used for a surface protection film of a semiconductor element or an interlayer insulating film, Si, SiO ₂ ,
A structure having a siloxane bond is introduced into the polyimide skeleton for the purpose of improving the adhesiveness to an inorganic underlayer film such as Si ₃ N ₄ or a metal for forming a circuit such as Al or Cu, or a silane coupling agent or Ti type It has been customary to add a coupling agent, an Al coupling agent or the like. However, when the polyimide resin film is exposed to the dry etching process of punching the inorganic passivation film during the semiconductor manufacturing process, the adhesiveness between the polyimide surface and various metals or the sealing resin is extremely reduced, and the semiconductor There is a problem that the reliability of the device is significantly reduced.

[0006]

The object of the present invention is to lower the molecular weight of amine residues in polyamic acid and to introduce a mono- or polyfunctional photosensitive group and a lower alcohol into the carboxyl group by covalent bonding. By adding a specific organosilicon compound, a photopolymerization initiator and / or a photosensitizer to the above polyamic acid ester, a fine pattern having excellent adhesiveness can be easily obtained.

[0007]

The present invention provides (A) a polyamic acid ester having a structure represented by the following general formulas (1a), (1b) and (1c), and (B) a general formula (2). A photosensitive resin containing an organosilicon compound, (C) a photopolymerization initiator and / or a photosensitizer as essential components, and further coating the above-mentioned photosensitive resin composition on a substrate,
This is a fine pattern forming method in which light is irradiated through a mask after drying on a heating plate at ℃, and the unexposed portion is removed with an organic solvent containing a cyclic ketone as a main component.

[0008]

[Chemical 6] R _5: 2 to 6-valent organic group R _6: ─H or ─CH ₃ each _{R 1, R 2, R 3} , R 4, R 5, R 6 are each an independent, be the same or different May be. p: integers 1 to 5 x, y, z: percentage of each structural unit, 0 <x and y <1
00, 0 <z <80 and x + y + z = 100
》

[0009]

[Chemical 7]

The polyamic acid ester comprising the structural units represented by the formulas (1a), (1b) and (1c) used in the present invention exhibits high reactivity and can obtain a pattern with high resolution. Formulas (1a), (1b) and (1c)
Among them, R ₁ is introduced from a compound having a tetravalent aromatic residue, and usually an aromatic tetracarboxylic acid or its derivative is mainly used. For example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3 , 3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, naphthalene-
2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride,
Naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6 7-
Hexahydronaphthalene-1,2,5,6, -tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3
5,6,7-hexahydronaphthalene-2,3,6,7
-Tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,7-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1 , 4,5,8-tetrachloronaphthalene-2,
3,6,7-tetracarboxylic dianhydride, 3,3 ′,
4,4'-diphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic Acid dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ",
4 ″ -p-terphenyltetracarboxylic dianhydride,
2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) Ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (2,2
3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic Acid dianhydride, perylene-3,4,9,10-
Tetracarboxylic dianhydride, perylene-4,5,10,
11-tetracarboxylic dianhydride, perylene-5,6
11,12-Tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2 , 9,10-Tetracarboxylic acid dianhydride, Pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, Pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, Thiophene-2, 3,4,5-tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic dianhydride and the like,
It is not limited to these. In addition, one kind or a mixture of two or more kinds may be used.

In formulas (1a), (1b), and (1C),
R ₂ is a divalent organic group having a molecular weight of R ₂ group (average molecular weight in a mixture of 2 or more kinds) of 160 or less, and a diamine and / or its derivative is usually used for its introduction. When the molecular weight exceeds 160, not only the crosslink density is lowered, but also the dissolving power in the developing solution is increased, swelling is likely to occur, and the resolution is lowered, which is not preferable. More preferable molecular weight is
It is 100 to 150. For example, the R ₂ group has a molecular weight of 16
Examples of the diamine having 0 or less include m-phenylenediamine,
p-phenylenediamine, 2,5-diamino-toluene, 3,5-diamino-toluene, 2,4-diamino-
Toluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2,5-diamino-
1,3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2-dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene- Diamine, hexamethylene-diamine, 2,5-dimethyl-hexamethylene-diamine,
3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene-
Diamine, 3-methyl-heptamethylene-diamine,
Examples thereof include 2,6-diamino-4-carboxylic benzene, but are not limited thereto. Among them, m-phenylenediamine, p-phenylenediamine,
2,5-diaminotoluene, 3,5-diaminotoluene, p-xylene-2,5-diamine, m-xylene-
2,5-diamine and p-xylene-2,6-diamine are preferable because of their higher resolution after development.

[0012] Also, R ₂ together with the low molecular weight diamines described above, in combination with the diamine molecular weight of R ₂ groups exceeds 160, better results are obtained by adjusting the average molecular weight to 160 or less. In this case, the R ₂ group has a molecular weight of 16
It is preferable to contain 15% by weight or more of a low molecular weight diamine which is 0 or less. If it is less than 15% by weight, the effect of improving the resolution is small and it is not preferable. The weight% of R _{2 in} the present invention is calculated by converting the R ₂ groups present in the polyamic acid ester into diamines. That is, it is determined by [weight of H ₂ N—R ₂ —NH ₂ ] / [weight of polyamic acid ester represented by formula (1a), (1b), (1c)] × 100 (%). As the diamine having these R ₂ groups exceeding 160,
For example, 4,4'-diamino-diphenylpropane,
3,3'-diamino-diphenylpropane, 4,4'-
Diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4 '
-Diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether,
3,3'-diamino-diphenyl ether, 3,3'-
Dimethyl-4,4'-diamino-biphenyl, 3,3 '
-Dimethoxy-benzidine, 4,4'-diamino-p-
Terphenyl, 3,3 ″ -diamino-p-terphenyl, bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ- Aminopentyl) benzene,
p-bis (2-methyl-4-amino-pentyl) benzene, p-bis (1,1-dimethyl-5-amino-pentyl) benzene, 1,5-diamino-naphthalene, 2,6
-Diamino-naphthalene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminopropyl)
Tetramethyldisiloxane, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4
-Aminophenoxy) phenyl] sulfone, 4,4 '
-Bis [4- (4-aminophenoxy) phenoxy] diphenyl sulfone, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4 '
-Diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 2,6-diamino-4-carboxylic benzene (methacrylic acid-2-hydroxyethyl) ester and the like, but are not limited thereto. is not. In use, one kind or a mixture of two or more kinds may be used. Among them, 4,4'-diaminodiphenyl ether, 1,3-bis (3-aminopropyl)
Tetramethyldisiloxane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2'-bis [4
-(4-aminophenoxy) phenyl] propane was added to R ₂
It is preferable to use it as a part of the group because the resolution is not lowered so much and the adhesion of the film at the time of curing is improved.

In the formulas (1a), (1b) and (1c), R
₃ is a photosensitive group having 1 to 5 acrylic (methacrylic) groups, R ₄ is a photosensitive group having 1 to 5 acrylic (methacrylic) groups, or a methyl group or an ethyl group. R
_When the acryl (methacryl) group in ₃ and R ₄ is 0, a crosslinked structure cannot be obtained, which is not preferable. Further, 6 or more acryl (methacryl) groups are not preferable because not only they are industrially difficult to produce but also the compatibility is lowered because the molecular weight becomes large. Examples of the compound for introducing R ₃ and R ₄ include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, Glycerol diacrylate, glycerol dimethacrylate, glycerol acrylate methacrylate, trimethylolpropane diacrylate, 1,3-diacryloylethyl-5-hydroxyethyl isocyanurate, 1,3-dimethacrylate-5
-Hydroxyethyl isocyanurate, ethylene glycol-modified pentaerythritol triacrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, glycidyl Examples thereof include, but are not limited to, acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol-modified methacrylate, polyethylene glycol-modified acrylate, polypropylene glycol-modified methacrylate and the like. In using these, one kind or a mixture of two or more kinds may be used. The methyl group or ethyl group of R ₄ is usually derived from methanol, ethanol or the like.
R ₅ is a divalent to hexavalent organic group obtained by removing a hydroxyl group and an acryloyloxy group or a methacryloyloxy group from the compound for introducing R ₃ or R ₄ described above, and among these, preferred is 2 It is a trivalent aliphatic group.

In the polyamic acid ester comprising the structural units represented by the formulas (1a), (1b) and (1c) used in the present invention, the ratio of the structural unit (1a) in which R ₃ is introduced into the carboxyl group is x, R ₃ is a part of the carboxyl group,
The ratio of the structural unit (1b) in which R ₄ is introduced into the rest is y,
The ratio of the structural unit (1c) in which the carboxyl group was substituted with R ₄ was z, and three types of structural units were mixed. 0 <x, y <100, 0 <z <80, respectively
And satisfying x + y + z = 100, x, y,
z represents the molar percentage of each structural unit. When R ₄ is a methyl group or an ethyl group, when z is 80 or more, the amount of the photosensitive group is small, the sensitivity is low and the practicality is low. The polyamic acid ester in the present invention is usually synthesized as follows. First, a compound having an alcohol group for introducing the polyfunctional photosensitive groups R ₃ and R ₄ is dissolved in a solvent, and excess acid anhydride or its derivative is reacted with this. After this, the remaining carboxyl group, the acid anhydride group,
It can be synthesized by reacting a diamine. In the reaction with a diamine, there are a method using carbodiimides as a condensing agent (JP-A-60-228537) and a method described in JP-A-6-313039, but the method is not particularly limited.

The organosilicon compound of the present invention is used for exhibiting good adhesion between the patterned polyimide and the inorganic passivation film, the circuit-forming metal and the semiconductor sealing resin. Its structure is a compound represented by the general formula (2), and its preparation method is usually a silane coupling agent having an amino group dissolved in a suitable polar organic solvent by dissolving tetracarboxylic acid dianhydride under stirring and cooling. It is easily obtained by adding 2 mol of tetracarboxylic acid dianhydride to amidation reaction. Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-glycidoxydimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldimethoxysilane, γ −
Aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane and the like. As an example of the tetracarboxylic acid dianhydride, the same one as the tetracarboxylic acid dianhydride containing the R ₁ residue which is a constituent component of the polyamic acid ester described above can be used. Silane coupling agent,
The tetracarboxylic dianhydride may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, the organosilicon compound represented by the general formula (2) is preferably used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polyamic acid ester. If the amount is less than 0.01 parts by weight, the effect of improving adhesion to metal, inorganic, and semiconductor encapsulation resins cannot be obtained, and if it exceeds 10 parts by weight, the heat resistance of the polyimide film that has been pattern-formed and subjected to the final curing treatment may deteriorate. However, the mechanical strength is lowered, and the adhesiveness itself is lowered, which is not preferable. The photopolymerization initiator and photosensitizer used in the present invention are added in order to improve lithographic properties such as sensitivity and resolution.
Examples of photosensitizers

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18]

[0028]

[Chemical 19]

Examples thereof include, but are not limited to: When used, one kind or a mixture of two or more kinds may be used. The addition amount of the photopolymerization initiator or the photosensitizer is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyamic acid ester. If it is less than 0.1 part by weight, the amount of addition is too small and it is difficult to obtain the effect of improving sensitivity. Two
If the amount exceeds 0 parts by weight, the strength of the cured film decreases, which is not preferable.

In the present invention, a storability improver can be added for the purpose of improving the storability. As the storage stability improver, 1-phenyl-5-mercapto-1H-tetrazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, pentaerythritol tetrakis- (thioglycolate), thioglycolic acid , Ammonium thioglycolate, butyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, trimethylolpropane tris- (thioglycolate), ethylene glycol dithioglycolate, β-mercaptopropionic acid, β-mercaptopropionic acid Octyl, trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakis- (β-thiopropionate), 1,4-butanediol dithiopropionate , Thiosalicylic acid, furfuryl mercaptan,
Benzyl mercaptan, α-mercaptopropionic acid,
p-hydroxythiophenol, p-methylthiophenol, thiophenol, p-methylphenol, 2,6
Examples thereof include, but are not limited to, -t-butylphenol and catechol.

In the present invention, a photopolymerizable monomer having a carbon-carbon double bond may be added for the purpose of further improving the sensitivity. For example, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate,
1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, N-methylol acrylamide , N, N-dimethyl acrylamide and acrylates thereof, or acrylamides in which acrylamide is changed to methacrylate or methacrylamide can be used.

To the photosensitive resin composition according to the present invention, an adhesion aid such as a silane coupling agent, an inhibitor, a leveling agent and various fillers may be added. The photosensitive resin composition of the present invention is used by dissolving it in a polar organic solvent. Examples of these organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfoxide, 3-methoxybutanol, acetic acid-3.
-Methoxybutyl, methyl lactate, ethyl lactate, butyl lactate, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethyl cellosolve,
Examples thereof include, but are not limited to, butyl cellosolve, ethyl carbitol, diethyl carbonate, cyclohexanone, methylcyclohexanone, diisobutyl ketone, cyclopentanone, butyl acetate and nitrobenzene. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether acetate, cyclopentanone and dimethyl sulfoxide are preferable. Also, one kind or a mixture of two or more kinds may be used.

In the method for producing a relief pattern using the photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, ceramic, or aluminum substrate. The coating method is spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Then 60-180 ℃
Dry the coating at moderate temperature. Examples of the drying method include an oven, an infrared furnace, and a heating plate, but the heating plate is preferable from the viewpoint of efficiency and easy temperature control. When drying with this hot plate, 8
It is preferable to dry at 0 to 130 ° C. If the temperature is lower than 80 ° C, the drying is insufficient, which is not preferable. On the other hand, if the temperature exceeds 130 ° C, drying becomes excessive, which is not preferable. More preferably, the temperature is 100 to 120 ° C. for 2 to 4 minutes, and then the desired pattern shape is irradiated with actinic radiation. As actinic radiation, X
Rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are particularly preferable. In order to obtain a pattern with higher resolution, it is more preferable to use an i-line stepper using a wavelength of 365 nm or a g-line stepper using a wavelength of 436 nm.

Next, the unirradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. As the developing solution, cyclic ketones such as cyclopentanone and cyclohexanone are preferable because they improve the resolution. Further, in order to adjust their solubility, isopropyl alcohol, xylene, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, butyl acetate, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-
You may add dimethylacetamide, dimethylsulfoxide, etc. The addition amount is preferably 50% by weight or less. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. As the rinse liquid, toluene,
Xylene, ethanol, methanol, isopropyl alcohol, butyl acetate, propylene glycol methyl ether acetate, water, etc. can be used. Subsequently, heat treatment is performed to form an imide ring, and a final relief pattern having high heat resistance is obtained. The heat treatment is usually carried out in an oven, a heating plate, an oven or the like, but it is desirable to cure in an inert atmosphere of nitrogen, carbon dioxide, argon or the like in order to reduce coloring after curing. The final curing temperature is 300 ° C.
Above 400 ℃ is preferable, but it takes enough time to reach the final curing temperature, or 150 ℃, 250 ℃
For example, it is desirable to cure at a low temperature and then cure.
The photosensitive resin composition according to the present invention is useful not only for semiconductor applications, but also as an interlayer insulating film for multilayer circuits, a cover coat for flexible copper clad boards, a solder resist film, a liquid crystal alignment film, and the like.

[0035]

The present invention will be described in detail with reference to the following examples. Example 1 322.2 g (1.0 mol) of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 228.3 g (1.0 mol) of glycerol dimethacrylate, and 32.0 g of methanol ( 1.0 mol) was suspended in N-methyl-2-pyrrolidone to give 166.1 g of pyridine.
(2.1 mol) was added and reacted at 25 ° C. for 10 hours.
Next, after 270.2 g (2.0 mol) of 1-hydroxy-1,2,3-benzotriazole was added and completely dissolved in 1 hour, N-methyl- was added while keeping the reaction system at 10 ° C or lower.
412.6 g (2.0 mol) of dicyclohexylcarbodiimide dissolved in 400 g of 2-pyrrolidone was added dropwise over about 20 minutes. Then, the reaction was carried out at 25 ° C. for 3 hours. P-xylene-2,5-diamine was added to the reacted reaction solution in an amount of 1
29.39 (0.95 mol) was added, and the reaction was carried out at 30 ° C. for 5 hours. After dicyclohexylurea was filtered off, the reaction mixture was reprecipitated in methanol, the solid was collected by filtration, washed with methanol, and dried under reduced pressure for 48 hours. When the molecular weight of the obtained solid was measured by GPC, the weight average molecular weight was 24,000. Furthermore, this obtained polymer 1
00 g was dissolved in 200 g of N-methyl-2-pyrrolidone, and 0.1 g of methyl ether hydroquinone and N-
Phenylglycine 5 g, 1-phenyl-5-mercapto-1H-tetrazole 1 g, 3- (2-benzimidazolyl) -7-diethylaminocoumarin 0.5 g, trimethoxysilylpropyl methacrylate 2 g, tetraethylene glycol dimethacrylate 10 g were added. , And γ-aminopropyltrimethoxysilane and 3,3 ′,
1.0 g of an organosilicon compound obtained by reacting with 4,4'-benzophenone tetracarboxylic acid dianhydride was added and dissolved at room temperature.

The obtained composition was applied onto a silicon wafer with a spinner and dried at 100 ° C. for 3 minutes to obtain a film having a thickness of 9 μm. A mask for measuring resolution (Toppan Test Chart No. 1) manufactured by Toppan Printing Co., Ltd. is overlaid on this film.
Irradiation with ultraviolet rays of 00 mJ / cm ² followed by development with cyclopentanone as a developer and rinsing with propylene glycol methyl ether acetate gave a resolution of 7
A μm pattern was formed. Separately, a spinner was coated on a silicon wafer in the same manner, dried at 100 ° C. for 3 minutes, exposed to ultraviolet light of 200 mJ / cm ^{2 on} the entire surface, further developed, rinsed, and then dried at 150 ° C. and 250 ° C. in a nitrogen displacement dryer.
It was cured at 350 ° C. for 30 minutes each. After that, the wafer is divided into two, and one is plasma etching equipment O manufactured by Tokyo Ohka Kogyo Co.
Using PM-EM1000, 100 W, 10 minutes (1 t
orr and O ₂ flow rate: 100 cssm). Sumitomo Bakelite Co., Ltd.'s epoxy-based semiconductor encapsulating material "Sumicon EME-6300H" was transfer-molded on these final cured polyimide coatings under conditions of 175 ° C and 2 minutes, vertical 2 mm, horizontal 2 mm, and height 2
mm molded articles and 10 pieces each were obtained with or without plasma treatment.
After post-curing at 175 ° C. for 4 hours, five shear peel strength tests were performed on the side of the molded product as shown in FIG. 1 with a Tensilon universal testing machine to test the interface between the molded product and the polyimide interface or the polyimide and silicon wafer interface. When the adhesive strength was measured, the average value without plasma treatment was 5.1 kgf / mm ² , and the average value with plasma treatment was 4.8 kgf / mm ² . For each of the remaining 5 molded products, 120 ° C, 2.1
Atm pressure cooker (PCT) treatment 100
After applying the time mean value 3.5 kgf / mm ² without plasma treatment was measured similarly bonding strength, to obtain a mean value 3.3 kgf / mm ² of there plasma treatment.

Example 2 The glycerol dimethacrylate and methanol of Example 1 were changed to 260.2 g (2.0 mol) of 2-hydroxyethyl methacrylate, and the reaction charge ratio and reaction conditions were exactly the same as in Example 1. As a result, a polymer having a weight average molecular weight of 23,000 was obtained. To this polymer was added 1.5 g of an organosilicon compound obtained by reacting γ-aminopropylmethyldiethoxysilane with 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride, and then added Example 1. Similarly, the results of patterning evaluation and adhesive strength measurement by adding a photopolymerization initiator and the like are shown in Table 1.
Got the result.

Example 3 P-xylene of Example 1
2,5-diamine was added to P-phenylenediamine 102.6
When changed to g (0.95 mol) and the reaction charging ratio and the reaction conditions were exactly the same as in Example 1, the weight average molecular weight was 2
50,000 polymers were obtained. Example 1 with this polymer
Table 1 shows the results obtained by adding the same organosilicon compound, photopolymerization initiator and the like to the patterning evaluation and measuring the adhesive strength. Example 4 The P-xylene-2,5-diamine of Example 1 was converted into 79.7 g (0.75 mol) of P-phenylenediamine and bis [4- (4-aminophenoxy) phenyl].
A reaction was performed in the same manner as in Example 1 except that the amount of sulfone was changed to 86.5 g (0.20 mol), and the weight average molecular weight was 31,
000 polymers were obtained. Table 1 shows the results obtained by adding the same organosilicon compound and photopolymerization initiator as in Example 1 to this polymer, evaluating the patterning, and measuring the adhesive strength. Example 5 The P-xylene-2,5-diamine of Example 1 was reduced to 40.9 g (0.30 mol), and 4,4 ′ was further added.
-Diaminodiphenyl ether 120.1 g (0.60
Mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane 12.4 g (0.05 mol) except that the reaction was performed in the same manner as in Example 1 to obtain a polymer having a weight average molecular weight of 29,000. Got To this polymer, the same organosilicon compound and photopolymerization initiator as in Example 1 were added,
The results of patterning evaluation and adhesive strength measurement are shown in Table 1.

Example 6 P-xylene of Example 1
The 2,5-diamine was reduced to 64.7 g (0.475 mol), and 4,4'-diaminodiphenyl ether 95.
A reaction was performed in the same manner as in Example 1 except that 1 g (0.475 mol) was added to obtain a polymer having a weight average molecular weight of 28,000. Table 1 shows the results obtained by adding the same organosilicon compound and photopolymerization initiator as in Example 1 to this polymer, evaluating the patterning, and measuring the adhesive strength. << Example 7 >> The reaction was performed in the same manner as in Example 1 except that P-xylene-2,5-diamine of Example 1 was changed to 122.58 g (0.90 mol), and the weight average molecular weight of 15,000 A polymer was obtained. Example 1 with this polymer
Table 1 shows the results obtained by adding the same organosilicon compound, photopolymerization initiator and the like to the patterning evaluation and measuring the adhesive strength.

Example 8 322.2 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (1.
22 mol of glycerol dimethacrylate
(1.0 mol), 32.0 g of methanol (1.0 mol) and γ-butyrolactone were suspended, and pyridine 166.
1 g (2.1 mol) was added and reacted at 25 ° C. for 10 hours. While maintaining the reaction system at 10 ° C. or lower, 412.6 g (2.0 mol) of dicyclohexylcarbodiimide dissolved in 400 g of γ-butyrolactone was added dropwise over about 20 minutes. Then, the mixture was stirred at 25 ° C for 30 minutes, then P-xylene-2,5-diamine (129.39, 0.95 mol) was added, and the mixture was reacted at 25 ° C for 5 hours. After dicyclohexylurea was filtered off, the reaction mixture was reprecipitated in methanol, the solid was collected by filtration, washed with methanol, and dried under reduced pressure for 48 hours to obtain a polymer having a weight average molecular weight of 20,000. Table 1 shows the results obtained by adding the same organosilicon compound and photopolymerization initiator as in Example 1 to this polymer, evaluating the patterning, and measuring the adhesive strength. << Examples 9 to 20 >> The varnishes obtained in Examples 1 to 4 were
Patterning evaluation was performed by changing the temperature and time of the heating platen during coating and also changing the developing solution. In each case, a high-resolution pattern was obtained. The results are shown in Tables 2 and 3.

Comparative Example 1 Patterning evaluation was conducted in the same manner as in Example 1 except that the organosilicon compound was not added.
The results of measuring the adhesive strength are shown in Table 4. << Comparative Example 2 >> Table 4 shows the results of patterning evaluation and adhesive strength measurement performed in the same manner as in Example 5, except that the organosilicon compound was not added. << Comparative Example 3 >> Table 4 shows the results of the patterning evaluation and the adhesive strength measurement performed in the same manner as in Example 1 except that the addition amount of the organosilicon compound was 12 g.

Comparative Example 4 P-xylene of Example 1
2,5-diamine was changed to 4,4'-diaminodiphenyl ether 190.2 g (0.95 mol),
The reaction was carried out in the same manner as in Example 1, and the weight average molecular weight was 2
8,000 polymers were obtained. Example 1 with this polymer
Table 4 shows the results obtained by adding the same organosilicon compound, photopolymerization initiator and the like to the patterning evaluation and measuring the adhesive strength. Comparative Example 5 From the composition of Example 1, N-phenylglycine, 1-phenylmercapto-1H-tetrazole, 3
A composition excluding-(2-benzimidazolyl) -7-diethylaminocoumarin was obtained and subjected to patterning evaluation in the same manner as in Example 1, but a clear pattern was not obtained even when the exposure amount was increased to 1000 mJ / cm ² . . << Comparative Examples 6 to 9 >> The composition of Example 1 was used to perform patterning while changing the hot platen temperature, time, and processing conditions of the developing solution. No high resolution pattern was obtained in either case. The results are shown in Table 5.

Table 1 Example 2 3 4 5 6 7 8 Resolution (μm) 7 7 8 7 7 6 7 7 Adhesive strength (kgf / mm ² ) No plasma treatment Normal condition 4.5 4.3 4.7 5.2 4.5 4.2 4.5 PCT 100hr after treatment 3.0 2.9 3.7 4.1 3.3 2.8 3.1 With plasma treatment Normal 4.0 3.8 4.4 3.5 3.9 3.7 3.8 After PCT100hr treatment 2.8 2.7 3.3 2.6 2.9 2.6 2.7

Table 2 Example 9 10 11 12 13 14 Resin used (Example) 1 1 1 1 1 2 Hot plate temperature (° C.) 115 90 100 100 100 115 Hot plate time (min) 3 4 3 3 3 3 3 Developer resolution ( μm) 6 8 6 7 7 6 Table 3 Example 15 16 17 18 19 20 Resin used (Example) 2 3 3 4 4 4 Hot plate temperature (° C) 100 115 100 115 100 100 Hot plate time (min) 3 3 3 3 3 3 3 Developer resolution ( μm) 6 6 7 7 8 8

Table 4 Comparative Example 1 2 3 4 5 Resolution (μm) 8 7 7 12 ー Adhesive strength (kgf / mm ² ) Without plasma treatment Normal 3.2 4.3 3.6 4.7 4.5 After PCT100hr treatment 0 1.8 1.1 3.4 3.3 With plasma treatment Normal 1.6 1.6 1.3 3.8 3.4 After PCT 100hr treatment 0 0.7 0.6 3.0 2.7

[0046] Note: * mark cannot be developed

Developer used: cyclopentanone: cyclopentanone / propylene glycol methyl ether acetate = 80/20 (weight ratio): cyclopentanone / propylene glycol methyl ether acetate = 60/40 (weight ratio): cyclopenta Non / γ-butyrolactone = 80/2
0 (weight ratio): cyclohexane: N-methyl-2-pyrrolidone: cyclopentanone / propylene glycol methyl ether acetate = 30/70 (weight ratio)

[0048]

By using the composition and pattern forming method of the present invention, it is possible to obtain a polyimide pattern which is extremely fine and has excellent adhesiveness.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a molded product showing a method for a shear peel strength test.

Front page continuation (51) Int.Cl. ⁷ identification code FI G03F 7/075 521 G03F 7/075 521 H01L 21/027 H01L 21/30 502R (56) Reference JP-A-5-289334 (JP, A) JP-A-6-342211 (JP, A) JP-A-7-5688 (JP, A) JP-A-59-116746 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/00-7/42

Claims (5)

(57) [Claims] 1. A polyamic acid ester represented by the following general formula (1a), (1b) and (1c), (B) an organosilicon compound represented by the following general formula (2), and (C) photopolymerization. A photosensitive resin composition comprising an initiator and / or a photosensitizer as essential components. [Chemical 1] R _5: 2 to 6-valent organic group R _6: ─H or ─CH ₃ each _{R 1, R 2, R 3} , R 4, R 5, R 6 are each an independent, be the same or different May be. p: integers 1 to 5 x, y, z: percentage of each structural unit, 0 <x and y <1
00, 0 <z <80 and x + y + z = 100
>> [Chemical 2] 2. R ₂ in the polyamic acid ester represented by formulas (1a), (1b) and (1c) is represented by the following formula (3):
The photosensitive resin composition according to claim 1, comprising at least one selected from the group consisting of at least 15% by weight. [Chemical 3] 3. A photosensitive resin composition of the remaining R ₂ in claim 2 according to claim 2, wherein at least one selected from the following formula (4). [Chemical 4] 4. The photosensitive resin composition according to claim 1, wherein the organosilicon compound is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polyamic acid ester. 5. The photosensitive resin composition according to claim 1 is coated on a substrate, dried on a hot plate at 80 to 130 ° C., and then irradiated with light through a mask to contain a cyclic ketone as a main component. A method for forming a fine pattern, which comprises removing an unirradiated portion with an organic solvent.