JP3342298B2 - Photosensitive resin composition - 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 having excellent adhesion and good storage stability.

[0002]

2. Description of the Related Art Conventionally, surface protection films and interlayer insulation films of semiconductor devices have excellent heat resistance and excellent electrical insulation properties.
Polyimide having mechanical strength or the like is used, but a technique for imparting photosensitivity to polyimide itself has recently attracted attention in order to simplify a complicated process of forming a polyimide pattern. For example,

[0003]

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[0004] A polyimide precursor composition having a photosensitive group provided with an ester group having a structure as shown in (for example, Japanese Patent Publication No. 55-41422) is known. These are all dissolved in an appropriate organic solvent, applied in a varnish state, dried, and then irradiated with ultraviolet light through a photomask.
A polyimide film is obtained by developing and rinsing to obtain a desired pattern, and further heating. The use of polyimide with photosensitivity not only has the effect of simplifying the pattern forming process, but also eliminates the need to use an etchant having a problem in the working environment, so it is safe and excellent in terms of pollution. Photosensitization is expected to become an even more important technology in the future.

When a polyimide resin is used for a surface protection film or an interlayer insulating film of a semiconductor element, Si, SiO ₂ , S
For the purpose of improving the adhesion to an inorganic base film such as i ₃ N ₄ or a metal for forming a circuit such as Al or Cu, a structure having a siloxane bond in a polyimide skeleton may be introduced, or a silane-based coupling agent, a Ti-based Usually, a coupling agent, an Al-based coupling agent and the like are added. However, if the polyimide resin film is exposed to a dry etching process of punching an inorganic passivation film during a semiconductor manufacturing process, the adhesiveness between the polyimide surface and various metals or sealing resins is extremely reduced, and the semiconductor device There is a problem that the reliability as a whole is greatly reduced.

[0006]

SUMMARY OF THE INVENTION The present invention provides a photosensitive resin composition having good storage stability and good adhesion.

[0007]

The present invention relates to (A) two or more acid dianhydrides having different reactivities with an alcohol having an unsaturated bond, wherein the acid dianhydride having a lower reactivity is used. And the reaction with the alcohol having an unsaturated bond, prior to the other acid dianhydride, sequentially add the more reactive acid dianhydride, react with the alcohol having an unsaturated bond, Then, a diamine is reacted with the following general formula (1)
a), polyamic acid esters represented by (1b) and (1c), (B) an organosilicon compound represented by the following general formula (2), and (C) a photopolymerization initiator and / or a photosensitizer are essential. It is a photosensitive resin composition characterized by being a component.

Embedded image (Wherein R _{1 is a} tetravalent aromatic residue and is a mixture of two or more R ₂ : a divalent organic group R ₅ : divalent to hexavalent organic group R ₆ : R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ of —H or —CH ₃ are each independent and may be the same or different. Is also good. p: integer of 1 to 5 x, y, z: percentage of each structural unit, 0 <x, y <10
0, 0 <z <80, and x + y + z = 100)

Embedded image (Wherein R ₇ : a tetravalent aromatic residue, which may be the same as or different from R ₁ ) R ₈ : a divalent organic group R ₉ , R ₁₀ : a monovalent organic group, independently of each other And may be the same or different 1: 0, 1 or 2) and preferably the organosilicon compound is present in an amount of 0.1 to 100 parts by weight of the polyamic acid ester.
The photosensitive resin composition according to the above, wherein the content is from 0.01 to 10 parts by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Two or more acid dianhydrides having different reactivity with an alcohol having an unsaturated bond used in the present invention are used in combination, and an acid dianhydride having a lower reactivity is combined with an unsaturated bond. The reaction with the alcohol having, prior to the other acid dianhydrides, sequentially add the more reactive acid dianhydride, react with the alcohol having an unsaturated bond, then react with the diamine The polyamic acid ester comprising the structural units represented by the formulas (1a), (1b) and (1c) has high reactivity and can obtain a high-resolution pattern.

In the formulas (1a), (1b) and (1c), R
₁ is introduced from a compound having a tetravalent aromatic residue, and usually an aromatic tetracarboxylic acid or a derivative thereof is mainly used. For example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic 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 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 (2,3-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 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 dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride,
Pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic anhydride But are not limited to these.

[0010] Two or more of these acid dianhydrides are used in combination. In this case, those having low reactivity with the alcohol having an unsaturated bond are replaced with alcohols having an unsaturated bond prior to other acid dianhydrides. It is necessary to react with. Without considering this, when acid dianhydrides having different reactivity with alcohol having an unsaturated bond are simultaneously reacted with the alcohol, the acid dianhydride with lower reactivity is not completely reacted with the alcohol. The unreacted product or one of the acid anhydride groups remains in the reaction system in a reacted state, and in a condensation reaction with a diamine, a three-dimensional reaction is likely to occur.
When a photosensitive resin composition is prepared by blending a photopolymerization initiator, a photosensitizer and the like, the storage stability is extremely lowered, which is not preferable. However, a photosensitive resin composition using a polyimide precursor having a photosensitive group obtained by simply reacting two or more kinds of tetracarboxylic dianhydrides with an alcohol having an unsaturated bond is stored at room temperature. There was a problem that stability was reduced.

For R _{2 in} formulas (1a), (1b) and (1C), diamines and / or derivatives thereof are usually used for the introduction. For example, as the diamine of the R ₂ group,
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-
Examples include, but are not limited to, dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 2,6-diamino-4-carboxylic benzene, and the like. Among them, m-phenylenediamine,
p-phenylenediamine, 2,5-diamino-toluene, 3,5-diamino-toluene, p-xylene-2,
5-diamine, m-xylene-2,5-diamine, p-
Xylene-2,6-diamine is mentioned.

Also, 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-diphenylsulfide, 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] diphenylsulfone, 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-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. Not something. These may be used alone or as a mixture.

R in the formulas (1a), (1b) and (1c)
₃ is a photosensitive group having 1 to 5 acryl (methacryl) groups, R ₄ is a photosensitive group having 1 to 5 acryl (methacryl) 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, six or more acryl (methacrylic) groups are not only difficult to produce industrially, but also have a large molecular weight, and thus are not preferred because compatibility is lowered. As the compound for introducing R ₃ and R ₄ , for example, 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-hydroxyethylisocyanurate, 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 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. These may be used alone or as a mixture. Further, the methyl group or ethyl group of R ₄ is usually derived from methanol, ethanol and the like, respectively. 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 , and among these, preferred are It is a trivalent aliphatic group.

The polyamide acid ester comprising the structural units represented by the formulas (1a), (1b) and (1c) used in the present invention has a ratio of the structural unit (1a) in which R ₃ is introduced into the carboxyl group as x, R ₃ is part of the carboxyl group,
The proportion of the structural unit (1b) into which R ₄ has been introduced is y,
The ratio of the structural unit (1c) in which the carboxyl group is substituted with R ₄ is z, and three types of structural units are mixed. 0 <x, y <100, 0 <z <80, respectively
And satisfy x + y + z = 100, and x, y,
z indicates the mole 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 practicability is low. The polyamic acid ester used 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,
This is reacted with an excess of an acid dianhydride or a derivative thereof.
At this time, as described above, when two or more acid dianhydrides are used in combination, it is necessary to react an acid dianhydride having lower reactivity with an alcohol having an unsaturated bond prior to another acid dianhydride. It is. In this case, it is known that the reactivity with the alcohol is generally higher for an acid dianhydride having an electron-withdrawing substituent. For example, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride or bis (3,4-
Dicarboxyphenyl) sulfone dianhydride.
Conversely, it is known that the reactivity of an acid dianhydride having an electron donating substituent with an alcohol is generally low. For example,
And bis (3,4-dicarboxyphenyl) ether dianhydride. To explain the reaction method specifically, when bis (3,4-dicarboxyphenyl) ether dianhydride and pyromellitic dianhydride are used in combination, first, bis (3,4-dicarboxy) having lower reactivity is used. After adding a predetermined amount of phenyl) ether dianhydride and reacting for 5 hours, a predetermined amount of pyromellitic dianhydride is added and reacted. Thereafter, the compound can be synthesized by reacting the remaining carboxyl group with a diamine. In the reaction with a diamine, a method using a carbodiimide as a condensing agent (Japanese Patent Application Laid-Open No. 60-228537) or Japanese Patent Application Laid-Open No. 6-3130
There is a method described in Japanese Patent Publication No. 39, but it is not particularly limited.

The organosilicon compound of the present invention is used to exhibit good adhesion between a patterned polyimide and an inorganic passivation film, a metal for forming a circuit, and a sealing resin for a semiconductor. The structure is a compound represented by the general formula (2). As a method for preparing the compound, usually, 1 mol of dicarboxylic dianhydride is dissolved in an appropriate polar organic solvent, and the silane cup having an amino group is stirred and cooled. It can be easily obtained by adding 2 mol of a ring agent to dicarboxylic dianhydride and performing an amidation reaction. In the formula (2), R ₇ is a compound having a divalent aromatic,
Or a compound having a divalent organic group, and its dicarboxylic acid is usually mainly used. Examples include phthalic anhydride and maleic anhydride, but are not limited thereto. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-
Aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropyldiethylmethoxysilane, γ
-Aminopropyldiethylethoxysilane, N- (β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 4-aminobutyl And dimethylmethoxysilane. The silane coupling agent and dicarboxylic anhydride may be used alone or in combination of two or more. In the photosensitive resin composition of the present invention, the amount of the organosilicon compound represented by the general formula (2) is 0.1 to 100 parts by weight of the polyamic acid ester.
It is preferable to add from 01 to 10 parts by weight. If it is less than 0.01 part by weight, the effect of improving the adhesion to metals, inorganics, and semiconductor sealing resins cannot be obtained. If it exceeds 10 parts by weight, the heat resistance of the patterned and finally cured polyimide film decreases, On the other hand, if the mechanical strength is lowered and extended, the adhesiveness itself is lowered, which is not preferable.

The photopolymerization initiator and photosensitizer used in the present invention are added to improve the lithography characteristics such as sensitivity and resolution. Examples of the photopolymerization initiator and photosensitizer include:

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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However, the present invention is not limited to these. These may be used alone or as a mixture.
The addition amount of the photopolymerization initiator or the photosensitizer is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polyamic acid ester. If the amount is less than 0.1 part by weight, the added amount is too small, and it is difficult to obtain the effect of improving sensitivity. If the amount exceeds 20 parts by weight, the strength of the cured film is undesirably reduced.

In the present invention, a preservability improver can be added for the purpose of improving the preservability. Examples of the preservability improver include 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 include, but are not limited to, -t-butylphenol and catechol.

In the present invention, a photopolymerizable monomer having a carbon-carbon double bond can 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-dimethylacrylamide and those obtained by changing these acrylates and acrylamides to methacrylates and methacrylamides can be used.

The photosensitive resin composition according to the present invention may contain an adhesion aid such as a silane coupling agent, an inhibitor, a leveling agent, and various fillers. The photosensitive resin composition of the present invention is used by dissolving it in a polar organic solvent. 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 include, but are not limited to, butyl cellosolve, ethyl carbitol, diethyl carbonate, cyclohexanone, methyl cyclohexanone, diisobutyl ketone, cyclopentanone, butyl acetate, nitrobenzene, and the like. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether acetate, cyclopentanone, and dimethyl sulfoxide are preferred. These may be used alone or as a mixture.

In the method for producing a relief pattern using the photosensitive resin composition according to the present invention, the composition is first applied to a suitable support, for example, a silicon wafer, ceramic or aluminum substrate. The coating method is performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Then 60-1
The coating is dried at a temperature of about 80 ° C. As a drying method, there are an oven, an infrared furnace, a hot plate and the like, but a hot plate is preferable from the viewpoint of efficiency and easy temperature control. When drying with this hot plate, it is preferable to dry at 80 to 130 ° C. 80 ℃
If it is less than this, drying is insufficient, which is not preferable. 130 ° C
Exceeding the range is not preferred because drying becomes excessive. More preferably, it is 2 to 4 minutes at 100 to 120 ° C., and then the desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, 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 higher-resolution pattern, 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, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. As a developer, cyclopentanone, cycloketone such as cyclohexanone,
This is preferable for improving the resolution. In order to further 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
-Dimethylacetamide, dimethylsulfoxide and the like may be added. The addition amount is preferably 50% by weight or less.
As a developing method, a system such as spray, paddle, immersion, or ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. As the rinsing liquid, toluene, xylene, ethanol, methanol, isopropyl alcohol, butyl acetate, propylene glycol methyl ether acetate, water and the like can be used. Subsequently, a 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 hot plate, a furnace or the like.
It is desirable to cure under an inert atmosphere such as carbon dioxide or argon. The final curing temperature is 300 ° C or higher,
The temperature is preferably 400 ° C. or lower, but it is desirable to take sufficient time before reaching the final curing temperature, or to cure at a low temperature such as 150 ° C. or 250 ° C. and then cure. The photosensitive resin composition according to the present invention is used not only for semiconductors,
It is also useful as an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film, and the like.

Hereinafter, the present invention will be described specifically with reference to examples. << Example 1 >> Bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter abbreviated as ODPA) 155.1
g (0.5 mol) in glycerol dimethacrylate 22
8.3 g (1.0 mol), methanol 32.0 g (1.
0 mol) was suspended in N-methyl-2-pyrrolidone, 166.1 g (2.1 mol) of pyridine was added, and the mixture was reacted at 25 ° C. for 5 hours. Thereafter, 161.1 g (0.5 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA) was added, and the mixture was further reacted for 10 hours. Next, 270.2 g (2.0 mol) of 1-hydroxy-1,2,3-benzotriazole was added and completely dissolved in 1 hour, and then N-methyl-2-pyrrolidone was maintained while maintaining the reaction system at 10 ° C. or lower. 412.6 g (2.0 mol) of dicyclohexylcarbodiimide dissolved in 400 g was added dropwise over about 20 minutes. Thereafter, the reaction was performed at 25 ° C. for 3 hours. 4,4'-Diaminodiphenyl ether (hereinafter abbreviated as DDE) was added to the reaction solution after the reaction.
0.2 (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 was measured by GPC, it was 25,000 in weight average molecular weight.
Further, 100 g of the obtained polymer was added to N-methyl-
Dissolved in 200 g of 2-pyrrolidone, 0.1 g of methyl ether hydroquinone and 5 g of N-phenylglycine,
1-phenyl-5-mercapto-1H-tetrazole 1
g, 3- (2-benzimidazolyl) -7-diethylaminocoumarin (0.5 g) and tetraethylene glycol dimethacrylate (10 g), and γ-aminopropyltriethoxysilane and 3,3 ′, 4,4′-benzophenonetetra 1.0 g of an organosilicon compound obtained by reacting with carboxylic dianhydride was added and dissolved at room temperature.
The varnish was allowed to stand at room temperature for 2 weeks, and the storage stability was examined. As a result, gelling did not occur and the varnish was stable.

The obtained composition was applied on a silicon wafer with a spinner and dried at 100 ° C. for 3 minutes to obtain a 9 μm thick film. A mask for measuring resolution (Toppan Test Chart No. 1) manufactured by Toppan Printing Co., Ltd.
Irradiation with ultraviolet light of 200 mJ / cm ² , development with cyclopentanone as a developing solution, and rinsing with propylene glycol methyl ether acetate gave a pattern with a resolution of 7 μm. Separately, a spinner is applied to a silicon wafer in the same manner, dried at 100 ° C. for 3 minutes, exposed entirely with ultraviolet rays of 200 mJ / cm ² , further developed, rinsed, and then dried at 150 ° C., 250 ° C.
Cured at 350 ° C. for 30 minutes each. Thereafter, the wafer was divided into two parts, and one of them was subjected to treatment using a plasma etching apparatus OPM-EM1000 manufactured by Tokyo Ohka Kogyo Co., Ltd. at 100 W for 10 minutes (1 torr, O ₂ flow rate: 100 csm). On the final cured polyimide film, an epoxy semiconductor encapsulating material "Sumicon EME-6300H" manufactured by Sumitomo Bakelite Co., Ltd. was transfer-molded at 175 ° C. for 2 minutes, 2 mm long and 2 m wide.
m, 2 mm high molded product with or without plasma treatment
Got a piece. After post-curing at 175 ° C. for 4 hours, five shear-peel strength tests were performed on the side of the molded article as shown in FIG. 1 using a Tensilon universal testing machine, and the interface between the molded article and the polyimide interface or between the polyimide and the silicon wafer interface was tested. When the adhesive strength was measured, the average without plasma treatment was 5.1 kgf / m.
m ² , average value with plasma treatment is 4.9 kgf / m
m ² . For each of the remaining 5 molded products, 12
0 ° C, 2.1atm pressure cooker (PCT)
After 100 hours of the treatment, the adhesive strength was measured in the same manner to obtain an average value of 3.8 kgf / mm ² without plasma treatment and an average value of 3.3 kgf / mm ² without 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 24,000 was obtained. An organosilicon compound obtained by reacting this polymer with γ-aminopropyltriethoxysilane and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
5 g was added, and a photopolymerization initiator and the like were further added in the same manner as in Example 1 to evaluate storage stability, patterning evaluation, and adhesive strength. Table 1 shows the results. << Embodiment 3 >> Instead of ODPA of Embodiment 1, 3, 3 '
The reaction charge ratio and reaction conditions were changed to 147.1 g (0.5 mol) of 4,4'-diphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA) in exactly the same manner as in Example 1, and the weight was reduced. A polymer having an average molecular weight of 26,000 was obtained. The same organosilicon compound, photopolymerization initiator, and the like as in Example 1 were added to this polymer, and storage stability evaluation, patterning evaluation, and adhesive strength were measured. Table 1 shows the results.

Example 4 Pyromellitic anhydride (hereinafter abbreviated as PMDA) 1 in place of BTDA in Example 1
Example 1 except that the amount was changed to 09.1 g (0.5 mol).
Was carried out in the same manner as in the above to obtain a polymer having a weight average molecular weight of 31,000. The same photopolymerization initiator as in Example 1 was added to this polymer, and γ-glycidoxypropylmethyldiethoxysilane and bis (3,4-dicarboxyphenyl) were further added.
1.0 g of an organosilicon compound obtained by reacting with ether dianhydride was added, and storage stability evaluation, patterning evaluation, and adhesive strength were measured. Table 1 shows the results. << Example 5 >> 180.2 g (0.9%) of DDE of Example 1
Mol), and 12.4 g (0.05 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added. A polymer was obtained. The same organosilicon compound, photopolymerization initiator, and the like as in Example 1 were added to this polymer, and storage stability evaluation, patterning evaluation, and adhesive strength were measured. Table 1 shows the results.

Comparative Example 1 Evaluation of storage stability was carried out in the same manner as in Example 1 except that no organosilicon compound was added.
Patterning evaluation and adhesive strength were measured. Table 1 shows the results. << Comparative Example 2 >> The storage stability evaluation, the patterning evaluation, and the adhesive strength were measured in the same manner as in Example 5 except that no organosilicon compound was added. Table 1 shows the results. << Comparative Example 3 >> Storage stability evaluation, patterning evaluation, and adhesion strength were measured in the same manner as in Example 1 except that the addition amount of the organosilicon compound was changed to 12 g. Table 1 shows the results. << Comparative Example 4 >> From the composition of Example 1, N-phenylglycine, 1-phenylmercapto-1H-tetrazole,
A composition excluding-(2-benzimidazolyl) -7-diethylaminocoumarin was obtained, and patterning was evaluated in the same manner as in Example 1. However, even when the exposure was increased to 1000 mJ / cm ^{2, a} clear pattern was not obtained. . << Comparative Example 5 >> The same operation as in Example 1 was conducted except that ODPA and BTDA were simultaneously reacted with glycerol dimethacrylate and methanol, and storage stability evaluation, patterning evaluation, and adhesive strength were measured. Table 1 shows the results. << Comparative Example 6 >> All operations were performed in the same manner as in Example 1 except that the order in which ODPA and BTDA were reacted with glycerol dimethacrylate and methanol was evaluated, and storage stability evaluation, patterning evaluation, and adhesive strength were measured. Table 1 shows the results.

[0040]

[Table 1]

[0041]

The photosensitive resin composition of the present invention is extremely excellent in storage stability, and can easily obtain a fine polyimide pattern having excellent adhesiveness.

[Brief description of the drawings]

FIG. 1 is a schematic view of a molded product in a shear peel strength test.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-27834 (JP, A) JP-A-6-342211 (JP, A) JP-A-6-83054 (JP, A) JP-A-6-83054 JP 51512 (JP, A) JP 5-134407 (JP, A) JP 5-127384 (JP, A) JP 63-15847 (JP, A) JP 9-222729 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (2)

(57) [Claims] (A) An acid dianhydride having a different reactivity with an alcohol having an unsaturated bond is used in combination of two or more, and an acid dianhydride having a lower reactivity is combined with an alcohol having an unsaturated bond. The reaction is performed prior to other acid dianhydrides, and the acid dianhydride having the higher reactivity is sequentially added, reacted with an alcohol having an unsaturated bond, and then reacted with a diamine. Formulas (1a), (1b) and (1
The polyamic acid ester represented by c), (B) an organosilicon compound represented by the following general formula (2), and (C) a photopolymerization initiator and / or a photosensitizer are essential components. Photosensitive resin composition. Embedded image (Wherein R _{1 is a} tetravalent aromatic residue and is a mixture of two or more R ₂ : a divalent organic group R ₅ : divalent to hexavalent organic group R ₆ : R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ of —H or —CH ₃ are each independent and may be the same or different. Is also good. p: integer of 1 to 5 x, y, z: percentage of each structural unit, 0 <x, y <10
0, 0 <z <80, and x + y + z = 100) (Wherein R ₇ : a tetravalent aromatic residue, which may be the same as or different from R ₁ ) R ₈ : a divalent organic group R ₉ , R ₁₀ : a monovalent organic group, independently of each other And may be the same or different 1: 0, 1 or 2) 2. The photosensitive resin composition according to claim 1, wherein the amount of the organosilicon compound is 0.01 to 10 parts by weight based on 100 parts by weight of the polyamic acid ester.