JP3040866B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition which is easy to produce, has high sensitivity, and gives a uniform coating film.

[0002]

2. Description of the Related Art As a heat-resistant photosensitive material, photosensitive polyimide is widely used for insulating films and passivation films of semiconductors. In many cases, polyimide or a precursor thereof has a photosensitive group introduced therein, or a polyimide precursor has a compound having a photosensitive group mixed therein. As an example of the former,
In JP-A-41422, a photosensitive group is added to an ester side chain of a polyamic acid. In JP-A-60-6029, a diamine having a double bond is synthesized in advance, and a photosensitive polyimide is prepared using this diamine. Have been proposed. However, these methods are not preferred because the steps for introducing a photosensitive group are complicated.
Further, Japanese Patent Application Laid-Open Nos.
No. 100143 discloses that an unsaturated epoxy compound or unsaturated isocyanate is added to a carboxyl group of a polyamic acid.
However, a method of reacting a carboxyl group of a polyamic acid with an epoxy group or an isocyanate group has been proposed. Have. Examples of the latter polyimide precursor mixed with a compound having a photosensitive group include, for example, JP-A-63-206741, JP-A-59-15449, and JP-A-2-144439.
JP-A No. 2-144439 or JP-A-2-144439 proposes a composition in which a polyamic acid and a compound having a photoreactive unsaturated group are mixed. Usually, these unsaturated group-containing compounds are mixed with a polyamic acid. Due to poor compatibility, use conditions are limited, making it difficult to use. On the other hand, JP-A-54-1
In a method of mixing a compound containing a double bond and an amino group or a quaternized salt thereof with a polyamic acid as disclosed in Japanese Patent No. 45794, the compatibility is good, but the sensitivity is low and cracks are generated during development. There is a problem. JP-A-3-917
In Japanese Patent Publication No. 52, special polyfunctional aminoacrylates are used, and sensitivity and cracks during development are improved, but such polyfunctional aminoacrylates are difficult to obtain as commercial products. The present inventors have conducted various studies in order to solve the above-mentioned problems relating to the known art. As a result, it was found that by using specific acrylamide glycolic acids as a photosensitive group, a photosensitive resin composition in which the various problems described above were solved was obtained, and the present invention was completed based on the knowledge. . As is clear from the above description, the object of the present invention is that the solution viscosity during the reaction with the polyamic acid is appropriate, the compatibility between the unsaturated group-containing compound and the polyamic acid is good, and the occurrence of cracks during development And a method of using the same without using a photosensitive resin composition.

[0003]

The present invention has the following configuration (1). (1) a poly (amide) imide precursor containing a repeating unit represented by the general formula (I); (2) acrylamidoglycolic acid represented by the general formula (II); and (3) a photoinitiator and / or
Or a photosensitive resin composition comprising a sensitizer as an essential component.

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Embedded image In the general formulas (I) and (II), R ¹ represents a trivalent or tetravalent organic group; R ² represents a divalent organic group;
Is 1 or 2, R ³ and R ⁴ are independently a methyl group,
It is an ethyl group or a hydrogen atom.

The structure and effect of the present invention will be described in detail below. In the case described above, acrylamidoglycolic acids are particularly preferable when R ³ and R ⁴ are hydrogen atoms in the formula (II).

A poly (amide) imide precursor containing a repeating unit represented by the general formula (I) is a polyamideimide precursor when n = 1 and a polyimide precursor when n = 2. R ¹ is a trivalent or tetravalent organic group, such as an aromatic group, an alicyclic group or an aliphatic group. R ² is a divalent organic group, such as an aromatic group, an alicyclic group, an aliphatic group, a heterocyclic group or a polysiloxane group. General formula (I)
Poly (amide) which is a polymer containing a repeating unit represented by
The imide precursor can be easily produced by reacting a tetracarboxylic dianhydride, a tricarboxylic anhydride or a derivative thereof with a diamine in a solvent by a conventional method.

The following compounds may be mentioned as specific examples of the tetracarboxylic dianhydride used in the present invention, but are not necessarily limited thereto. That is, examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyltetraanhydride. Carboxylic dianhydride, 2,3,3 ', 4'-
Biphenyltetracarboxylic dianhydride, 3,3 ', 4
4'-benzophenonetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4-benzophenonetetracarboxylic dianhydride, bis- (3,4-dicarboxyphenyl) ether dianhydride , Bis- (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2 , 2-bis-
(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and the like. Examples of the alicyclic tetracarboxylic dianhydride include cyclobutanetetracarboxylic dianhydride and methylcyclobutanetetracarboxylic dianhydride. And as the aliphatic tetracarboxylic dianhydride,
1,2,3,4-tetracarboxybutane dianhydride and the like,
Known compounds can be mentioned.

A specific example of the tricarboxylic anhydride used in the present invention is trimellitic anhydride.

The following compounds can be mentioned as specific examples of the diamine used in the present invention, but are not necessarily limited thereto. That is, as the aromatic diamine, 4,4′-diaminodiphenyl ether, 3,3 ′
4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,
4′-diaminodiphenyl sulfide, 4,4′-di (methaminophenoxy) diphenyl sulfone,
4'-di (paraaminophenoxy) diphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, benzidine, 3,3'-
Diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-2,2-propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4'-bis (4-aminophenoxy )
Biphenyl, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 1,4-diaminotoluene, meta-xylylenediamine, 2,2′-dimethylbenzidine and the like, and examples of the aliphatic diamine include trimethylene diamine, tetramethylene diamine, hexamethylene diamine, and 2,11-dodecane diamine. Examples of the silicon-based diamine include bis (para-aminophenoxy) dimethylsilane and 1,4-bis (3-aminopropyldimethylsilyl) benzene. Examples of the alicyclic diamine include 1,4-diaminocyclohexane,
Examples of guanamines such as bis (4-aminocyclohexyl) methane and isophoronediamine include acetoguanamine and benzoguanamine. Also,
Examples of the diaminosiloxane include compounds represented by the following formula (where p in the formula is 1 to 100). Known diamines other than those shown above can also be used.

[0009]

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In the present invention, the following compounds can be mentioned as specific examples of preferred solvents (hereinafter, sometimes referred to as reaction solvents) for reacting the above-mentioned starting compounds in a solvent. That is, N-methyl-2-pyrrolidone,
N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea,
Pyridine, hexamethylphosphoramide, methylformamide, N-acetyl-2-pyrrolidone, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, methylcyclopentanone, cyclohexanone, crezo-
Γ-butyrolactone, isophorone, N, N-diethylacetamide, N, N-diethylformamide,
N, N-dimethylmethoxyacetamide, tetrahydrofuran, N-methyl-ε-caprolactam, tetrahydrathiophene dioxide persulfolane (sulfo)
lane)｝. This reaction also involves the conversion of the organic solvent into another aprotic (neutral) organic solvent such as an aromatic, alicyclic or aliphatic hydrocarbon, or a chlorinated derivative thereof (eg, benzene, toluene, xylene). , Cyclohexane, pentane, hexane, petroleum ether, methylene chloride, etc.) or dioxane.

[0011] In the presence of the above solvent, by a known method,
A poly (amide) imide precursor can be synthesized from the acid anhydride and the diamine. In this case, aminosilane can be introduced into the polymer terminal for the purpose of improving the adhesion to the substrate.

Specific examples of such aminosilanes and the following compounds can be given, but are not necessarily limited thereto. That is, aminomethyl-di-n-propoxy-methylsilane, (β-aminoethyl) -n-
Propoxy-methylsilane, (β-aminoethyl) -diethoxy-phenylsilane, (β-aminoethyl) -tri-n-propoxysilane, (β-aminoethyl) -dimethoxy-methylsilane, (γ-aminopropyl) -di- n-propoxy-methylsilane, (γ-aminopropyl) -di-n-butoxy-methylsilane, (γ-aminopropyl) -triethoxysilane, (γ-aminopropyl) -di-n-pentoxy-phenylsilane, (γ -Aminopropyl) -methoxy-n-propoxy-methylsilane, (δ-aminobutyl) -dimethoxy-methylsilane, (3-aminophenyl) -di-n-propoxysilane, (4-aminophenyl) -tri-n-propoxy Silane, {β- (4-aminophenyl) ethyl} -diethoxy-methylsilane, {β -(3-aminophenyl) ethyl} -di-n-propoxy-phenylsilane, {γ-
(4-aminophenyl) propyl} -di-n-propoxy-methylsilane, {γ- (4-aminophenoxy) propyl} -di-n-propoxy-methylsilane, {γ-
(3-aminophenoxy) propyl} -di-n-butoxy-methylsilane, {γ- (3-aminophenoxy) propyl} -dimethyl-methoxysilane, (γ-aminopropyl) -methyl-diethoxysilane, (γ- (Aminopropyl) ethyl-di-n-propoxysilane, (4-aminophenyl) -trimethoxysilane, (3-aminophenyl) -trimethoxysilane, (4-aminophenyl) -methyl-dimethoxy-silane, (3- Known compounds such as (aminophenyl) -dimethyl-methoxysilane and (4-aminophenyl) -triethoxysilane can be exemplified.

[0013] In addition to these compounds, for the purpose of controlling the molecular weight of the poly (amide) imide precursor, 1
The reaction can also be carried out by adding a compound having two acid anhydride groups or amino groups. The following compounds can be exemplified as examples of such compounds.

Phthalic anhydride, maleic anhydride, aniline, monoallylamine, etc.

The following compounds may be mentioned as specific examples of the acrylamidoglycolic acids represented by the general formula (II), which are photosensitive components constituting the photosensitive resin composition of the present invention.

N- (carboxy, hydroxy) methylacrylamide (acrylamidoglycolic acid), N-
(1-carboxy, 1-hydroxy) ethyl acrylamide, N- (1-carboxy, 1-hydroxy) propyl acrylamide, N- (carboxy, hydroxy) methyl methacrylamide, N- (1-carboxy, 1-hydroxy) ethyl methacryl Amide, N- (1-carboxy, 1-hydroxy) propyl methacrylamide and the like.

The amount of the acrylamidoglycolic acid represented by the general formula (II) is 2 to 200% by weight, preferably 30 to 100% by weight of the poly (amide) imide precursor.
% By weight.

As the photopolymerization initiator or sensitizer used in the present invention, known compounds may be used, but one kind of them or a mixture of several kinds thereof may be used. Specific examples thereof are listed below, but are not limited thereto.

Benzophenone, Michler's ketone, 4,
4'-diethylaminobenzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropyl Propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, camphor-quinone, benzuanthrone , 2-methyl-1- {4- (methylthio) phenyl}
-2-morpholino-1-propane, 3,3 ', 4,
4'-tetra (t-butylperoxycarbonyl) benzophenone, N-phenyl-glycine, p-hydroxy-N-phenylglycine, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, p-tolyl disulfide, 4-dimethylaminobenzoic Ethyl acid, isoamyl 4-dimethylaminobenzoate, 3,3 '
-Carbonyl-bis (7-diethylamino) coumarin,
2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-
Methylcyclohexanone, 2,6-bis (p-azidobenzylidene) -4-t-butylcyclohexanone and the like.

The addition amount of the photopolymerization initiator is 0.05 to 20% by weight, preferably 0.5 to 10% by weight based on the poly (amide) imide precursor.

If necessary, a compound having a known carbon-carbon double bond of 50% by weight or less or a polyvalent thiol may be added as a crosslinking aid to the poly (amide) imide precursor. . Hereinafter, specific examples will be exemplified.

Butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, benzyl acrylate, carbitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate
, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate
N-methylolacrylamide, N-diacetoneacrylamide, N, N'-methylenebisacrylamide, N-vinylpyrrolidone, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, Butylene glyco-
Rudiacrylate, butylene glycol-dimethacrylate
G, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol dimethacrylate.
Pentaerythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetra (3-mercaptopropionate) ), Pentaerythritol (mercaptoacetate) and the like.

In addition, thermal polymerization inhibitors such as hydroquinone and p-methoxyphenol, or auxiliary materials such as dyes and pigments can be added.

Next, a method for forming a patterned poly (amide) imide film using the photosensitive polymer composition of the present invention will be described. The photosensitive polymer composition of the present invention can be applied to a substrate such as a silicon wafer, a metal plate, a plastic plate or a glass plate by a known method such as spin coating, dipping or spray printing. The coating film is heated to 30 to 1 by using a heating means such as an electric furnace or a hot plate.
Prebake at a temperature of 50 ° C. removes most of the solvent in the coating. A negative mask is placed on the coating film and irradiated with actinic radiation. X-rays, electron beams,
Examples include ultraviolet light, visible light, and the like,
Ultraviolet or far infrared radiation is particularly preferred. Next, the unexposed portion is dissolved and removed with a developing solution to obtain a relief pattern.
Get If necessary, rinse in a non-solvent,
Drying is carried out at a temperature of not more than ℃ to stabilize the relief pattern. At any point after prebaking, the film can be peeled off from the substrate and used as a single film. Since the polymer of the relief pattern formed by development is in the form of a precursor, it is heated to 200 to 500 ° C., preferably 30 ° C. by the above-mentioned heating means.
By heating at a temperature of 0 to 400 ° C., a patterned poly (amide) imide film is formed. In this case, the acrylamidoglycolic acid represented by the general formula (II), which is a compound containing a photosensitive group, is polymerized by actinic radiation to form a polymer. Volatilize. Thus, a patterned heat-resistant poly (amide) imide film can be obtained from the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention may be applied to electronic materials, but it may be used for a passivation film of a semiconductor device, an interlayer insulating film, an α-ray shielding film of an LSI memory, or an interlayer film of a multilayer film substrate. It is particularly preferable for an insulating film or an interlayer film of a multilayer board of a printed wiring board.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A 1-liter flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser, and a nitrogen purge device was purged with nitrogen gas, and then N-methyl-2-pyrrolidone (hereinafter referred to as N-methyl-2-pyrrolidone). (Abbreviated as NMP) 400
g, 70.59 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA)
(0.219 mol), 43.54 g of 4,4'-diaminodiphenyl ether (hereinafter abbreviated as DDE) (0.219 mol).
18 mol) and reacted at 20 to 25 ° C. for 20 hours to synthesize a polyamic acid solution. To this solution was added N- (carboxy, hydroxy) methylacrylamide 42.4.
g, 2.12 g of isopropylthioxanthone and 0.71 g of Michler's ketone were added and dissolved by stirring to prepare a photosensitive resin composition of the present invention.

Example 2 Using the same apparatus and method as in Example 1, 400 g of NMP and pyromellitic dianhydride 1
6.37 g (0.0751 mol), BTDA 24.18
g (0.0751 mol) and 30.04 g of DDE (0.
150 mol) were mixed to synthesize a polyamic acid solution.
To this solution are added 42.4 g of N- (carboxy, hydroxy) methylacrylamide, 1.41 g of 2,4-diethylthioxanthone and 1.41 g of Michler's ketone, and the mixture is dissolved by stirring to obtain a photosensitive resin composition of the present invention. Was prepared.

Example 3 Using the same apparatus and method as in Example 1, 400 g of NMP, 38.01 g (0.123 mol) of 4,4'-oxydiphthalic dianhydride, 2,2-bis {4- ( 4-aminophenoxy) phenyl @ hexafluoropropane 60.45 g (0.116 mol), 1,3
1.53 g (0.00614 mol) of -bis (3-aminopropyl) tetramethyldisiloxane was mixed to synthesize a polyamic acid solution. N- (carboxy,
The present invention is obtained by adding 50 g of hydroxy) methylacrylamide, 2.00 g of 2-methyl-1- {4- (methylthio) phenyl} -2-morpholino-1-propane and 1.00 g of Michler's ketone and stirring and dissolving. Was prepared.

Example 4 An N, N-dimethylacetamide (hereinafter referred to as DMAC) was prepared using the same apparatus and method as in Example 1.
400 g, hexafluoroisopropylidene-2,2-bis (phthalic anhydride) 10
9.28 g (0.246 mol), 39.0 g (0.238 mol) of 3,3′-diaminodiphenylsulfone and 3.15 g of 4-aminophenyltrimethoxysilane
(0.0148 mol) were mixed to synthesize a polyamic acid solution. 68.6 g of N- (carboxy, hydroxy) methylacrylamide and 2-methyl-1- {4
-(Methylthio) phenyl} -2-morpholino-1-
3.43 g of propane and 1.71 g of isopropylthioxanthone were added and dissolved by stirring to prepare a photosensitive resin composition of the present invention.

(Embodiment 5) Using the same apparatus and method as in Embodiment 1, 400 g of DMAC and 65.05 g of BTDA
(0.202 mol), ω, ω′-bis (3-aminopropyl) polydimethylsiloxane (molecular weight: 660)
00 g (0.0606 mol) and 28.08 g DDE
(0.141 mol) were mixed to synthesize a polyamic acid. To this solution, 66.7 g of N- (carboxy, hydroxy) methylacrylamide, 1.33 g of 2,4-diethylthioxanthone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholino-1-propane.2.
67 g and 1.33 g of Michler's ketone were added and dissolved by stirring to prepare a photosensitive resin composition of the present invention.

(Example 6) Using the same apparatus and method as in Example 1, 400 g of DMAC and diphenylsulfone-
3,3 ', 4,4'-tetracarboxylic dianhydride78.
77 g (0.220 mol) and 54.56 g (0.220 mol) of 3,3′-diaminodiphenyl sulfone were mixed to synthesize a polyamic acid. 66.7 g of N- (carboxy, hydroxy) methylacrylamide was added to this solution,
2.67 g of 2,4-diethylthioxanthone and 1.33 g of Michler's ketone were added and dissolved by stirring to prepare a photosensitive composition of the present invention.

(Embodiment 7) Using the same apparatus and method as in Embodiment 1, 400 g of DMAC and 46.11 g of BTDA
(0.143 mol), trimellitic chloride anhydride30.
21 g (0.143 mol) and 57.28 g DDE
(0.286 mol), and a polyamic acid solution was synthesized. 66.7 g of N- (carboxy, hydroxy) methylacrylamide, 2.67 g of 2,4-diethylthioxanthone and 1.33 g of Michler's ketone are added to this solution, and the mixture is stirred and dissolved to give the photosensitive composition of the present invention. Prepared.

(Example 8) The photosensitive resin composition of the present invention prepared in Examples 1 to 7 was spin-coated on a silicon wafer and prebaked on a hot plate at 100 ° C for 60 seconds. To form a more uniform film. Next, through a mask, exposure was performed by changing the irradiation time with an ultra-high pressure mercury lamp (20 mW / cm ² ). This was developed by immersing it in a mixed solution of 4 volumes of N-methyl-2-pyrrolidone and 6 volumes of isopropyl alcohol, rinsed in isopropyl alcohol, and dried. This at 200 ° C for 30 minutes,
Further, firing was performed at 350 ° C. for 1 hour in an electric furnace to obtain a patterned polyimide film. Table 1 shows the appropriate dose of the photosensitive resin composition prepared in each example, and the film thickness after prebaking and after development. From these results, it is clear that they are sufficiently practical.

[0035]

The photosensitive resin composition of the present invention can be easily produced by mixing a specific photosensitizer and a known photoinitiator with polyamic acid, and its practical effect is large.

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-221109 (JP, A) JP-A-3-170547 (JP, A) JP-A-3-288154 (JP, A) JP-A-3-3 293357 (JP, A) JP-A-55-160746 (JP, A) JP-A-62-195036 (JP, A) JP-A-63-227852 (JP, A) JP-A-62-295047 (JP, A) JP-A-57-190045 (JP, A) JP-A-3-137648 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/027 G03F 7/031 G03F 7/038 H01L 21/027

Claims (2)

(57) [Claims] (1) a poly (amide) imide precursor containing a repeating unit represented by the general formula (I), (2) a general formula (II)
A photosensitive resin composition comprising, as essential components, an acrylamide glycolic acid represented by the formula (1) and (3) a photoinitiator. Embedded image Embedded image In the general formulas (I) and (II), R ¹ represents a trivalent or tetravalent organic group; R ² represents a divalent organic group;
Is 1 or 2, R ³ and R ⁴ are independently a methyl group,
It is an ethyl group or a hydrogen atom. 2. The photosensitive resin composition according to claim 1, wherein R ³ and R ⁴ in the formula (II) are hydrogen atoms. Embedded image