JP3378379B2 - Photosensitive polyimide resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition.
More specifically, a highly sensitive photosensitive polyimide resin set
About adult. 2. Description of the Related Art In the process of manufacturing semiconductor devices,
In addition, photoresist plays a role in processes such as etching.
When the cracking is completed, it is separated and removed. But photoresist
The film is used as a surface protection film and interlayer insulation film for semiconductor devices
Electrical
And high mechanical properties are required. Furthermore, this
Unavailable film must withstand high temperatures applied in the semiconductor manufacturing process
Is also required. In recent years, photosensitive polymers have been
A mid-resin film is used. Polyimide resin is
Excellent in mechanical properties, mechanical properties, and heat resistance.
Used for surface protection film and inter-layer insulation film of semiconductor devices
However, selectively apply a polyimide resin film to fine parts
It is convenient to use photosensitive polyimide resin
It is. Conventionally, a polyimide resin has been selectively applied to fine parts.
As a method of applying a grease film, poly
Apply an imide resin film and coat the surface with photoresist.
Turn to form a polyimide resin film with hydrazine etc.
A method for etching is known. But this one
The method requires a complicated process and a highly toxic etching solution.
Must be used. In contrast, in recent years, light irradiation
For the photosensitive polyimide resin whose solubility changes with
Some suggestions have been made. Such photosensitive polyimide
As the resin, polyimide which is a precursor of a polyimide resin is used.
Compounds in which photopolymerizable acryloyl groups have been introduced into acrylic acid
It is a representative one (Japanese Patent Publication No. 55-30207,
No. 55-41422). Acryloyl group with salt structure
Polyimide precursors introduced in (1)
59-52822). [0004] The sensitivity of using such a polyimide precursor is
In the case of photosensitive polyimide resin, photosensitive polymer
After forming a polyimide resin film and forming a pattern with light,
The ring is closed and polyimide is formed by the treatment. At this time,
Part is separated and volatilizes, and the final film thickness decreases. Exposure
If a conductive polyimide resin is used,
Can be shortened. However, conventional photosensitivity
Polyimide resin has a complicated synthesis route,
When imidization, removal of photosensitive groups is not complete or complete
Disadvantages such as insufficient storage stability and exposure sensitivity
Had. Recently, actinic radiation represented by the following general formula
Group P ^* [0005] (Where n = 2 or 3, R ¹ = H, CH _Three , R ^Two = Organic
A) a polyamic acid compound having a residue at both ends. (Wherein, m = an integer of 10 to 10000, R ^Three , R ^Four = Aroma
Resin compositions containing an aromatic cyclic group) have been proposed.
(JP-A-4-70661, JP-A-4-77741)
issue). This photosensitive resin composition can be polymerized at the terminal.
Polymerization of polyamic acid having a stable carbon-carbon double bond
Amide compounds containing possible carbon-carbon double bonds in solvents
It is manufactured by a special method of reacting,
The reamic acid itself is photosensitive and the solvent itself is 1
It has the characteristic of being 00% photosensitive. This exposure
Resin composition has high sensitivity and excellent film properties
Have been. [0008] However, the policies disclosed in these publications are not disclosed.
In the case of riamic acid compounds, the terminal modifying group is easily released, and
Poor storage stability. The reason is that polyamic acid compounds
Aromatic tetracarboxylic anhydride as a raw material is usually
Carboxyl bonded to two adjacent carbon atoms
The group is dehydrated to form an acid anhydride type residue.
Therefore, the terminal-modified carboxyl group
Another carboxyl group derived from acid anhydride type residue at position G
Is present, but the carboxyl group at the ortho position
This is because the terminal modifying group is easily removed by the adjacent group effect.
It is estimated to be. [0009] The polyamic acid compound is commonly used.
Usually, a part of the acid anhydride is esterified with the actinic radiation functional group.
And then add diamine to form polymer
Obtained by the method. However, in this method, the molecular weight
Polyamic acid with large cracks is generated, and high molecular weight
It is difficult to synthesize only riamic acid. Further
In addition, the photosensitive resin composition described in these publications, the solvent is
Because it also serves as a photosensitizer, the composition is applied to a substrate,
When a film is formed by heat treatment,
The problem is that the residual stress on the
Was. SUMMARY OF THE INVENTION An object of the present invention is to provide a sensitivity
Excellent resist characteristics such as high storage stability
An object of the present invention is to provide an optical polyimide resin composition. Departure
To overcome the problems of the prior art,
As a result of intensive research on
Polyamic having a structure modified with a citric acid derivative
By using an acid compound, the above object can be achieved.
Was found. [0011] The polyamic acid compound of the present invention is a polyamic acid compound.
Inducing Trimellitic Acid with Specific Structure at the End of Mixic Acid
Storage stable due to the structure modified by the conductor
High sensitivity, high molecular weight, high sensitivity, and residual
Photosensitive polyimide resin group capable of forming low stress film
A composition can be provided. The present invention is based on these findings.
It was completed based on. [0012] Thus, according to the present invention,
For example, (A) a polyamic oxidation compound represented by the general formula (1)
[0013] [Wherein, R ¹ Is a tetravalent organic group, and R ^Two Is divalent
Is an organic group. k is an integer of 5 to 10,000.
Z is an actinic radiation functional group represented by the following formula (2). Embedded image (Where R ^Three , R ^Four , R ^Five , R ⁶ , And R ⁷ Is photopolymerizable
A substituent having a suitable carbon-carbon double bond. m is 0
Or 1. )] (B) a photosensitive auxiliary having a photopolymerizable functional group, and (C) a solvent.
Provided a photosensitive resin composition characterized by containing an agent
Is done. Hereinafter, the present invention will be described in detail. (A) Polyamic acid compound The polyamic acid compound used in the present invention is a diamine
Compounds such as trimellitic acid derivatives and tetracarboxylic acids
Or an acid anhydride thereof, and the mixture is subjected to a condensation reaction by a conventional method.
And is obtained by Polyamic acid used in the present invention
The compound is composed of a diamine compound and a trimellitic acid derivative.
To the mixture is added tetracarboxylic acid or its anhydride.
In addition, it can be obtained by a condensation reaction
Can be. According to these methods, stable high molecular weight
A polymer is obtained. <Diamine compound> Dia used in the present invention
As the min compound, for example, 2,2′-di (p-amino
Nophenyl) -6,6'-bisbenzoxazole,
2,2'-di (p-aminophenyl) -5,5'-bis
Benzoxazole, m-phenylenediamine, 1-a
Sopropyl-2,4-phenylenediamine, p-phenyl
Diamine, 4,4'-diaminodiphenylpropa
, 3,3'-diaminodiphenylpropane, 4,4 '
-Diaminodiphenylethane, 3,3'diaminodife
Nilethane, 4,4'-diaminodiphenylmethane,
3,3'-diaminodiphenylmethane, 4,4'-dia
Minodiphenyl sulfide, 3,3'-diaminodife
Nylsulfide, 4,4'-diaminodiphenylsulfo
3,3'-diaminodiphenylsulfone, 4,4 '
-Diaminodiphenyl ether, 3,3'-diaminodi
Phenyl ether, benzidine, 4,4 "-diamino-
p-terphenyl, 3,3 ″ -diamino-p-terphe
Nil, bis (p-aminocyclohexyl) methene, bis
(P-β-amino-t-butylphenyl) ether, bi
(P-β-methyl-δ-aminopentyl) benzene,
p-bis (2-methyl-4-aminopentyl) benze
, P-bis (1,1-dimethyl-5-aminopenty
B) benzene, 1,5-diaminonaphthalene, 2,6-
Diaminonaphthalene, 2,4-bis (β-amino-t-
Butyl) toluene, 2,4-diaminotoluene, m-ki
Silene-2,5-diamine, p-xylene-2,5-di
Amine, m-xylylenediamine, p-xylylenediamine
Aromatic diamines such as mines; 2,6-diaminopyridi
2,5-diaminopyridine, 2,5-diamino-
Heterocyclic diamines such as 1,3,4-oxadiazole
Alicyclic dia such as 1,4-diaminocyclohexane
Mines; piperazine, methylenediamine, ethylenedia
Min, propylenediamine, 2,2-dimethylpropyl
Diamine, tetramethylenediamine, pentamethylene
Diamine, hexamethylenediamine, 2,5-dimethyl
Hexamethylenediamine, 3-methoxyhexamethylene
Diamine, heptamethylenediamine, 2,5-dimethyl
Heptamethylenediamine, 3-methylheptamethylenedi
Amine, 4,4-dimethylheptamethylenediamine,
Ctamethylene diamine, nonamethylene diamine, 5-meth
Tyrnonamethylenediamine, 2,5-dimethylnonameti
Rangeamine, decamethylenediamine, 1,10-dia
Mino-1,10-dimethyldecane, 2,11-diamino
Dodecane, 1,12-diaminooctadecane, 2,12
-Diaminooctadecane, 2,17-diaminoicosa
And other diamines such as diaminosiloxanes
, 2,6-diamino-4-carboxylbenze
3,3'-diamino-4,4'-dicarboxy
Cubenzidine and the like. These diamine compounds
Objects can be used alone or in combination of two or more
Can be used. Among these, 2,2'-
Di (p-aminophenyl) -6,6'-bisbenzooxy
Sasol and 2,2'-di (p-aminophenyl)-
5,5'-bisbenzoxazole has low thermal expansion and high
It is particularly preferable because a heat-resistant polymer can be obtained. <Tetracarboxylic acid or acid anhydride thereof>
Tetracarboxylic acid or its anhydride used in the present invention
As, for example, pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic acid
Water, benzene-1,2,3,4-tetracarboxylic acid
Anhydride, 2,2 ', 3,3'-benzophenonetetraca
Rubonic anhydride, 2,3,3 ', 4'-benzopheno
Tetracarboxylic dianhydride, naphthalene-2,3
6,7-tetracarboxylic dianhydride, naphthalene-1,
2,5,6-tetracarboxylic dianhydride, naphthalene-
1,2,4,5-tetracarboxylic dianhydride, naphthale
1,2,5,8-tetracarboxylic dianhydride, naph
Taren-1,2,6,7-tetracarboxylic dianhydride,
4,8-dimethyl-1,2,3,5,6,7-hexahi
Dronaphthalene-1,2,5,6-tetracarboxylic acid
Anhydride, 4,8-dimethyl-1,2,3,5,6,7-
Hexahydronaphthalene-2,3,6,7-tetracar
Boric acid dianhydride, 2,6-dichloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, 2,7-dic
Loronaphthalene-1,4,5,8-tetracarboxylic diacid
Anhydride, 2,3,6,7-tetrachloronaphthalene-
1,4,5,8-tetracarboxylic dianhydride, 1,4
5,8-tetrachloronaphthalene-2,3,6,7-te
Tracarboxylic dianhydride, 3,3 ', 4,4'-dife
Nyltetracarboxylic dianhydride, 2,2 ', 3,3'-
Diphenyltetracarboxylic dianhydride, 2,3,3 ',
4'-diphenyltetracarboxylic dianhydride, 2,
3 ", 4,4" -p-terphenyltetracarboxylic acid
Anhydride, 2,2 ", 3,3" -p-terphenyltetra
Carboxylic dianhydride, 2,3,3 ", 4" -p-terf
Phenyltetracarboxylic dianhydride, 2,2-bis (2,
3-dicarboxyphenyl) -propane dianhydride, 2,
2-bis (3,4-dicarboxyphenyl) -propane
Dianhydride, bis (2,3-dicarboxyphenyl) A
Terdianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (2,3-dicarboxyphenyl)
B) methane dianhydride, bis (3,4-dicarboxyphene)
Nyl) methane dianhydride, bis (2,3-dicarboxy
Enyl) sulfone dianhydride, bis (3,4-dicarboxy)
(Ciphenyl) sulfone dianhydride, 1,1-bis (2,3
-Dicarboxyphenyl) ethane dianhydride, 1,1-bi
(3,4-dicarboxyphenyl) ethane dianhydride,
Perylene-2,3,8,9-tetracarboxylic dianhydride
, Perylene-3,4,9,10-tetracarboxylic acid
Anhydride, perylene-4,5,10,11-tetracarbo
Dianhydride, perylene-5,6,11,12-tetra
Carboxylic dianhydride, phenanthrene-1,2,7,8
-Tetracarboxylic dianhydride, phenanthrene-1,
2,6,7-tetracarboxylic dianhydride, phenanthrene
1,2,9,10-tetracarboxylic dianhydride
Aromatic Tetracarboxylic Dianhydride and Its Hydrogenation
Substance: cyclopentane-1,2,3,4-tetracarboxylic
Acid dianhydride, cyclobutanetetracarboxylic dianhydride,
Bicyclo [2,2,2] oct-7-en-2-ex
SO, 30 exo, 5-exo, 6-exotetracarbo
Acid 2,3: 5,6-dianhydride, bicyclo [2,2,
1] heptane-2-exo, 3-exo, 5-exo,
6-exotetracarboxylic acid 2,3: 5,6-dianhydride
Alicyclic acid anhydrides such as pyrazine-2,3,5,6-te
Tracarboxylic dianhydride, pyrrolidine-2,3,4,5
Tetracarboxylic dianhydride, thiophene-2,3
Heterocyclic derivatives such as 4,5-tetracarboxylic dianhydride
And the like. These are each alone or
Can be used in combination of two or more. this
Among them, pyromellitic dianhydride, 3,3 ', 4,
4'-benzophenonetetracarboxylic dianhydride, and
These combinations have good low thermal expansion, crack resistance
It is particularly preferable for realizing the resolution and the resolution. <Trimellitic acid derivative> In the present invention,
Both ends of the riamic acid compound are represented by the general formula (2).
Having a specific structure
Use trimellitic acid derivatives. That is, the following general formula
It is a trimellitic acid derivative of (3). Embedded image In the general formula (3), R ^Three , R ^Four , R ^Five , R ⁶ , And R ⁷ Is the light
A substituent having a polymerizable carbon-carbon double bond,
m is 0 or 1. Having a photopolymerizable carbon-carbon double bond
Examples of the substituent include an acryloyloxymethylene group and
Tacryloyloxymethylene group is typical
But also vinyl, propenyl, isopropene
Nil, butenyl, pentynyl, hexynyl, 2
-An alkenyl group having 2 to 6 carbon atoms such as an ethylbutenyl group
And its substituents. Alkenyl having 2 to 6 carbon atoms
Specific examples of the substituent that can be bonded to the group include a halogen atom
, Phenyl group, alkenyl group having 1 to 4 carbon atoms, carbon number
And 1-4 alkoxy groups. Such trimelli
The citrate derivative is, for example, an anhydride represented by the general formula (4).
Trimellitic acid halide and an alcohol represented by the general formula (5)
Alcohol with a dehydrohalogenation reaction (esterification reaction).
) Can be synthesized. Embedded image In the general formula (4), X is a halogen atom. Embedded image In the general formula (5), R ^Three , R ^Four , R ^Five , R ⁶ , And R ⁷ Is the light
A substituent having a polymerizable carbon-carbon double bond,
m is 0 or 1. The above reaction is usually carried out in an inert solvent in a base
Done in the presence of Methyl chloride is used as an inert solvent.
, Chloroform, trichloroethane, etc.
Hydrocarbons: pentane, hexane, cyclopentane,
Aliphatic hydrocarbons such as chlorohexane; benzene, tol
Aromatic hydrocarbons such as ene and xylene; acetonitrile
Nitriles; amines such as pyridine; dimethyl
Amides such as ruformamide and dimethylacetamide
Ethers such as tetrahydrofuran; acetone;
Ketones such as cyclopentanone are used. This
Of these, halogenated hydrocarbons are awarded. base
As trimethylamine, triethylamine, etc.
Alkylamines such as N, N-dimethylaniline;
Aromatic amines; pyridine, dimethylaminopyridine, etc.
And the like are used. Among them, Archi
Lumin is awarded. Use of alcohol represented by general formula (5)
The amount is the amount of trimellitic anhydride hara represented by the general formula (4).
Usually, 1 to 5 moles, preferably 1
１．５1.5 mol. The amount of the solvent used is determined by the general formula (4).
Trimellitic anhydride halide and alcohol of general formula (5)
The total amount is usually 2 to 20 times the weight of the total amount of salt
The amount of the group used is the amount of trimellitic anhydride hara of the general formula (4).
The amount is usually 1 to 5 mol per mol of the id, and is preferably
Or 1 to 3 moles. The reaction temperature is usually -10 to +
80 ° C., preferably -5 to + 30 ° C.
It is usually 0.5 to 24 hours, preferably 1 to 5 hours.
After the reaction is completed, trimellitic acid
Derivatives can be isolated. For example, chloroform
Recrystallization with a solvent such as tetrahydrofuran
Examples include reprecipitation and purification using a mixed solution with toluene.
Is shown. As a specific example of the above reaction, for example,
The merit acid halide is represented by the general formula (6): Using the compound of formula (I) as an alcohol, a compound represented by the general formula (7): (In the formula, R is a hydrogen atom or a lower alkyl group.
You. )), The use of a compound of the general formula (8) The trimellitic acid derivative represented by is obtained. As the alcohol represented by the general formula (7)
Is, for example, triacryloylpentaerythritol,
And trimethacryloyl pentaerythritol.
It is. In addition, the esterification reaction is usually carried out using m
-Place. Commonly used trimellitic acid derivatives
Trimellitic anhydride represented by formula (8)
[Tris (acryloyl) pentaerythritol] S
Ter [in general formula (8), when R = H], trimellit
Acid anhydride [tris (methacryloyl) penta
Erythritol] ester [In the general formula (8), R = methyl
Group, etc.), synthesis costs, operability, high sensitivity, high resolution
It is excellent in terms of image resolution and the like, and is particularly preferable. (B) Photosensitizer having photopolymerizable functional group Photosensitizers that can be used in the present invention are generally photocurable
There is no particular limitation as long as it is known as a nomer. Feeling
Pentaerythritol triacrylate as a photo aid
(Meth) acrylic acid-based compounds such as
is there. As the acrylic acid-based compound, for example, acrylic
Acid, methyl acrylate, ethyl acrylate, n-propyl
Propyl acrylate, isopropyl acrylate, n-
Butyl acrylate, isobutyl acrylate, cyclo
Hexyl acrylate, benzyl acrylate, rib
Tall acrylate, methoxyethyl acrylate, d
Toxyl ethyl acrylate, butoxyethyl acrylate
G, hydroxyethyl acrylate, hydroxypropyl
Ruacrylate, butylene glycol monoacrylate
G, N, N-dimethylaminoethyl acrylate, N,
N-diethylaminoethyl acrylate, glycidylua
Acrylate, tetrahydrofurfuryl acrylate, pe
Nantaerythritol monoacrylate, trimethylol
Propane monoacrylate, allyl acrylate, 1,
3-propylene glycol diacrylate, 1,4-butane
Tylene glycol diacrylate, 1,6-hexane
Recall diacrylate, neopentyl glycol dia
Acrylate, dipropylene glycol diacrylate,
2,2-bis- (4-acryloxydiethoxyphenyi
Le) propane, 2,2-bis- (4-acryloxypro
Pyroxyphenyl) propane, trimethylolpropane
Diacrylate, pentaerythritol dialk relay
G, trimethylolpropane triacrylate, penta
Erythritol triacrylate, triacryl forma
, Tetramethylol methane tetraacrylate,
Acrylic acid of ris (2-hydroxyethyl) isocyanuric acid
Luric ester, embedded image (In the formula, b represents an integer of 1 to 30.) (Where c and d represent integers where c + d = 2 to 30)
You. ), Embedded image Embedded image And the like. Examples of the methacrylic acid compound include, for example,
Methacrylic acid, methyl methacrylate, ethyl methacrylate
Rate, propyl methacrylate, isopropyl methacrylate
Relate, butyl methacrylate, isobutyl methacrylate
, Cyclohexyl methacrylate, benzyl meth
Acrylate, octyl methacrylate, ethylhexyl
Methacrylate, methoxyethyl methacrylate, eth
Xyethyl methacrylate, butoxyethyl methacrylate
, Hydroxyethyl methacrylate, hydroxyp
Ropyr methacrylate, hydroxybutyl methacrylate
G, hydroxypentyl methacrylate, N, N-dimethyl
Tylaminomethacrylate, N, N-diethylaminometh
Tacrylate, glycidyl methacrylate, tetrahydride
Rofurfuryl methacrylate, methacryloxypropyl
Trimethoxysilane, allyl methacrylate, trimethyl
Roll propane monomethacrylate, pentaerythritol
Monomethacrylate, 1,3-butylene glycol
Dimethacrylate, 1,6-hexane glycol dimeth
Acrylate, neopentyl glycol dimethacrylate
G, 2,2-bis- (4-methacryloxydiethoxyf
Enyl) propane, trimethylolpropane dimethacrylate
Rate, pentaerythritol dimethacrylate, tri
Methylol propane triacrylate, pentaerythri
Tall trimethacrylate, tetramethylol methanate
Tramethacrylate, tris (2-hydroxyethyl)
Methacrylic acid ester of isocyanuric acid, (In the formula, e represents an integer of 1 to 30.) (Where f and g are integers satisfying f + g = 1 to 30)
You. ), Embedded image Embedded image And the like. These compounds are each alone.
Alternatively, two or more kinds can be used in combination. This
Among them, in particular, pentaerythritol triacrylate
And the compound of the above formula (b = 3) is preferred.
No. The amount of photosensitizer used is compatible with the polyamic acid compound.
The amount of use is not particularly limited as long as
In the case of, by heat treatment of the polyamic acid compound
Difficult to decompose and remove during polyimideation, and remaining film
Stress increases, causing warpage and other deformation of the semiconductor element substrate
There is a problem that it becomes easier. Therefore, the photosensitizer
(A) 100 parts by weight of a polyamic acid compound
Usually, 10 to 40 parts by weight, preferably 15 to 35 parts by weight,
More preferably 20 to 30 parts by weight
Is desirable. (C) solvent As the solvent used in the present invention, for example, N-meth
Tyl-2-pyrrolidone, N, N-dimethylacetamide
, N, N-dimethylformamide, dimethyl sulfoxide
Sid, tetramethyl urea, trimethyl hexamethyl phosphate
And polar solvents such as γ-butyrolactone.
In addition to these polar solvents, acetone, methyl ethyl ketone
Tons, methyl isobutyl ketone, cyclohexanone, etc.
Ketones: methyl acetate, ethyl acetate, butyl acetate,
Esters such as diethyl borate and diethyl malonate;
Tyl ether, ethylene glycol dimethyl ether,
Diethylene glycol dimethyl ether, tetrahydro
Ethers such as furan; dichloromethane, 1,2-dic
Lorethane, 1,4-dichlorobutane, trichloroethane
Halogens such as benzene, chlorobenzene, o-dichlorobenzene, etc.
Hydrocarbons; hexane, heptane, octane, ben
Use hydrocarbons such as benzene, toluene, xylene, etc.
Can be These solvents may be used alone or
Can be used in combination of two or more. this
Among them, N, N-dimethylacetamide and N-methyl
Ru-2-pyrrolidone and the like are particularly preferred. Solvent usage
Is sufficient to dissolve each component uniformly. Special
The amount ratio sufficient to dissolve (A) the polyamic acid compound
Used in. The ratio of solvent used depends on the type of solvent and polyamide.
(A) polyamic acid
Usually, 3 to 25 times (weight ratio) to the compound is preferable.
5 to 20 times, more preferably 6 to 10 times.
You. (D) Photopolymerization initiator In the present invention, in addition to the components (A) to (C),
A photopolymerization initiator can be added as necessary. Photopolymerization
Examples of the initiator include Michler's ketone, benzoy
, 2-methylbenzoin, benzoin methyl ether
Benzoin ethyl ether, benzoin isopropyl
Ether, benzoin butyl ether, 2-t-butyl
Luanthraquinone, 1,2-benzo-9,10-ant
Raquinone, anthraquinone, methylanthraquinone,
4,4'-bis- (diethylamino) benzophenone,
Acetophenone, benzophenone, thioxanthone,
1,5-acenaphthene, 2,2-dimethoxy-2-fe
Nylacetophenone, 1-hydroxycyclohexylf
Phenyl ketone, 2-methyl- [4- (methylthio) phene
Nil] -2-morpholino-1-propanone, diacetyl
Benzyl, benzyldimethyl ketal, benzyldie
Tilketal, diphenyl disulfide, anthracese
, Phenanthrenequinone, riboflavin tetrabutyle
, Acrylic orange, erythrosine, phenanthre
Nquinone, 2-isopropylthioxanthone, 2,6-
Bis (p-diethylaminobenzylidene) -4-methyl
-4-azacyclohexanone, 6-bis (p-dimethyl
Aminobenzylidene) -cyclopentanone, 2,6-bi
(P-diethylaminobenzylidene) -4-phenyl
Cyclohexanone, aminostyryl keto represented by the following formula
[0043] 3-ketocoumarin compound represented by the following formula: (Where R ¹⁴ Is an aromatic carbon having 5 to 20 ring atoms
A ring or a heterocyclic ring; ¹¹ , R ¹² And R ¹³ Is it
Each independently represents a hydrogen atom, a hydroxyl group, a carbon number of 1 to 5
Alkyl groups, dialkylamino groups, alkoxy groups,
Or an acyloxy group. ), Bisque represented by the following formula
Marine compound (Where R ²⁰ And R ^{twenty one} Is independently a hydrogen atom,
An alkyl group having 1 to 5 carbon atoms, a dialkylamino group,
It is a lucoxy group or an acyloxy group. ), N-Fe
Nylglycine, N-phenyldiethanolamine, 3,
3 ', 4,4'tetra (t-butylperoxycarboni
Le) benzophenone and the like. Photopolymerization
The amount of the initiator used is not particularly limited.
Usually, 0 to 10 with respect to 100 parts by weight of the mic acid compound.
Parts by weight, preferably 0.1 to 5 parts by weight, more preferably
1 to 5 parts by weight. (E) Other additives The composition of the present invention may further contain, if necessary, an adhesion aid and a resin.
Use of various additives such as belling agents and polymerization inhibitors
Can be. [0047] Method of using photosensitive polyimide resin composition The method for using the photosensitive polyimide resin composition of the present invention is as described above.
Instead, the composition is applied to a suitable support, for example, a silicon wafer.
Or ceramic, aluminum substrate, etc. Application
Methods include spin coating using a spinner, spraying
Spray coating, dipping, printing, roll coating using a coater
And other methods. Next, at a low temperature of 60-80 ° C
After pre-baking and drying the coating, it is formed into the desired pattern shape
Irradiate the ray. X-rays, electron beams, ultraviolet rays
Line, visible light, etc. can be used.
Are preferred. Next, the non-irradiated portion is dissolved and removed with a developer.
Thus, a relief pattern is obtained. As a developer, N
-Methyl-2-pyrrolidone, N, N-dimethylacetoa
Polar solvents such as amide, N, N-dimethylformamide,
Methanol, isopropyl alcohol, water, etc.
They are used alone or in combination of two or more. Present
Imaging methods include spray, paddle, immersion, ultrasonic, etc.
Can be adopted. Relief pattern formed by development
Rinse. Methanol, ethanol, etc.
And isopropyl alcohol and butyl acetate.
I can do it. Next, a heat treatment is performed to form an imide ring,
Polyamic acid compound is converted to polyimide to provide high heat resistance
To get the final pattern. Photosensitive polyimide according to the present invention
Resin compositions are used not only for semiconductor device-related
Cover coat for circuit interlayer insulation film and flexible copper clad board
Also used as solder resist film and liquid crystal alignment film
can do. The present invention will be described in more detail with reference to the following examples.
Will be explained. Parts and% in Examples and Comparative Examples
Are by weight unless otherwise noted. [Synthesis Example 1] <Trimellitic anhydride [Tris (methacrylic acid)]
Loyl) pentaerythritol] Synthesis of Ester> Pen
Taerythritol trimethacrylate 5 mmol and anhydrous
5.1 mmol of trimellitic acid chloride was added to
In the presence of 5.1 mmol of triethylamine in styrene, 0
The mixture was reacted by stirring at 3 ° C. for 3 hours. Wash the reaction mixture with water
After drying over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure.
And reprecipitated with a mixed solvent of tetrahydrofuran and toluene.
The residue was purified and yielded 25% in trimellitic acid.
Hydride [Tris (methacryloyl) pentaeryth
Litol] ester was obtained. Example 1 2,2'-di (p
-Aminophenyl) -6,6'-bisbenzoxazo
115.5 g (0.276 mol), dimethylacetoa
552 g of amide and 552 g of N-methyl-2-pyrrolidone
It was charged to prepare a homogeneous liquid. Acidic anhydride under ice cooling and stirring
3,3 ', 4,4'-benzophenonetetraca
85.1 g (0.264 mol) of rubonic dianhydride, tri
Meric acid anhydride [Tris (methacryloy
Pentaerythritol] ester 11.3 g (0.
022 mol). Then, under ice cooling, 3
Reaction for 20 hours at room temperature,
A carboxylic acid compound was synthesized. The polyamic oxidation thus obtained
625.0 parts (100 parts in solid content) of 3,3 ',
4,4'-tetra (t-butylperoxycarbonyl)
Benzophenone (BTTB: λmax = 340 nm; day
2 parts, N-phenylglycine 2 parts, and feeling
VISCOAT 300 (manufactured by Osaka Organic Chemical Co., Ltd .:
28 parts of antaerythritol triacrylate)
And dissolved at room temperature. The resulting composition is applied to a silicon wafer
Apply on top with a spinner and dry at 60 ° C for 30 minutes
After drying, a film having a thickness of 14 μm was formed. The silicon wafer on which this film is formed
Then, using Toppan Printing's step tablet mask,
Exposure was performed using PLA-501F (manufactured by Canon Inc.).
With 70% N-methylpyrrolidone and isopropyl alcohol
Spray development with a developer consisting of a mixture of
went. As a result, the exposure energy was 750 mJ / cm.
^Two (436 nm)
did it. Also, the silicon wafer on which the same film is formed
(C) PLA using Toppan Printing's resolution evaluation mask
1200mJ / cm at -501F ^Two At the exposure energy
When exposed and developed in the same way, a pattern of 17 μm width was obtained.
Could be resolved. Example 2 2,2'-di (p-aminophen)
Enyl) -6,6'-bibenzoxazole 115.5
g (0.276 mol), trimellitic acid anhydride
Do [tris (methacryloyl) pentaerythritol]
11.3 g (0.022 mol) of ester, dimethylacetate
552 g of toamide and 552 g of N-methylvirolidone
Into a homogeneous solution of 3,3 ', 4,4'-ben
42.6 g of zophenone tetracarboxylic anhydride (0.1
32 mol) and 28.8 g of viromellitic dianhydride (0.
132 mol) was added as a powder in small portions. Next
For 3 hours under ice-cooling and 20 hours at room temperature. Profit
666.7 parts of the obtained polyamic acid (100
Part), 2 parts of BTTB (λmax = 340 nm), N-
Phenylglycine 2 parts, Biscoat 300 28 parts by weight
Was added and dissolved at room temperature. The obtained composition was spun on a silicon wafer.
And dried at 60 ° C for 30 minutes with a dryer.
A film of about 14 μm was obtained. This film has a letterpress stamp
Using a printing step tablet mask, PLA-501
F (manufactured by Canon) and exposed to N-methylpyrrolide
With 70% developer and 30% isopropyl alcohol
Play development was performed. As a result, the exposure energy becomes 75
0mJ / cm ^Two (436nm)
Could be obtained. Also, letterpress printing on the same film
1200m with PLA-501F using resolution evaluation mask
J / cm ^Two Exposure and development in the same way, 17 μm width
Could be resolved. Example 3 2,2'-di (p-aminophen)
Enyl) -6,6'-bibenzoxazole 115.5
g (0.276 mol), trimellitic acid anhydride
Do [tris (methacryloyl) pentaerythritol]
11.3 g (0.022 mol) of ester, dimethylacetate
552 g of toamide and 552 g of N-methylpyrrolidone
Into a homogeneous solution of 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride 8
5.1 g (0.264 mol) were added in small portions in powder form.
Then, the reaction was performed for 3 hours under ice cooling and for 20 hours at room temperature.
Was. 625.0 parts of the obtained polyamic acid (1
00 parts), 2 parts of BTTB (λmax = 340 nm),
N-phenylglycine 2 parts, 3EG-A (manufactured by Kyoeisha:
28 parts by weight of a compound of the formula (b) where b = 3)
Dissolved in warm. The obtained composition is spun on a silicon wafer.
And dried at 60 ° C for 30 minutes with a dryer.
A film of about 14 μm was obtained. This film has a letterpress stamp
Using a printing step tablet mask, PLA-501
F (manufactured by Canon) and exposed to N-methylpyrrolidone
Spray with 70% developer and 30% isopropyl alcohol
Lay development was performed. As a result, the exposure energy becomes 500
mJ / cm ^Two (436nm)
I got it. In addition, letterpress printing solution on the same film
750 mJ / with PLA-501F using an image quality evaluation mask
cm ^Two After exposure and development in the same manner, a 16 μm wide
It was resolved up to the turn. Comparative Example 1 No acid anhydride for terminal modification
Using 3.25 g (0.022 mol) of water phthalic acid,
Is 2,2'-di (p-aminophenyl) in the same manner as in Example 1.
1) -6,6'-bibenzoxazole 15.5 g
(0.276 mol), 552 g of dimethylacetamide,
And 552 g of N-methylbirrolidone in an ice-cooled solution.
Under stirring, 3,3 ', 4,4'-benzophenonetetracal
85.1 g (0.264 mol) of boric anhydride in small portions
Added in powder. Then, for 3 hours under ice-cooling and 20 hours at room temperature.
Allowed to react for hours. 650.0 parts of obtained polyamic acid
(100 parts in solid content), BTTB (λmax = 340)
nm) 2 parts, N-phenylglycine 2 parts, biscoat 3
28 parts by weight were added and dissolved at room temperature. The obtained composition is spun on a silicon wafer.
And dried at 60 ° C for 30 minutes with a dryer.
A film of about 16 μm was obtained. This film has a letterpress stamp
Using a printing step tablet mask, PLA-501
F (manufactured by Canon) and exposed to N-methylpyrrolidone
Spray with 70% developer and 30% isopropyl alcohol
Lay development was performed. As a result, to get the pattern
Exposure energy is 1200mJ / cm ^Two (436 nm)
This was necessary. Toppan printing resolution on the same film
1200mj with PLA-50JF
/ Cm ^Two Exposure and development in the same manner, but with a practical level of resolution
I didn't get a turn. [Comparative Example 2] Photosensitizer used in Example 1
The photosensitive composition was synthesized without adding Biscoat-300
Was. 2,2'-di (p-aminophenyl) -6,6'-
115.5 g of bibenzoxazole (0.276
Tris), trimellitic anhydride [Tris (meta)
Chryloyl) pentaerythritol] ester 11.3
g (0.022 mol), and dimethylacetamide 55
2 g, 552 g of N-methylbirrolidone in a homogeneous solution on ice
Under stirring, 3,3 ', 4,4'-benzophenonetetraca
85.1 g (0.264 mol) of rubonic anhydride was added in small portions
One powder was added. Then, at room temperature for 3 hours under ice cooling,
The reaction was performed for 0 hours. The obtained polyamic acid 625.0
BTTB (λmax = 34)
0 nm) and 2 parts of N-phenylglycine,
Dissolved at room temperature. The obtained composition is spun on a silicon wafer.
And dried at 60 ° C for 30 minutes with a dryer.
A film of about 17 μm was obtained. This film has a letterpress stamp
Using a printing step tablet mask, PLA-501
F (manufactured by Canon) and exposed to N-methylpyrrolidone
Spray with 70% developer and 30% isopropyl alcohol
Lay development was performed. Exposure energy is 1200mJ / c
m ^Two (436 nm), the film dissolves violently and the pattern
I couldn't get it. Comparative Example 3 N- as a solvent and a photosensitizer
Example except that dimethylacrylamide was used
The same operation as in Example 2 was performed. 2,2'-di (p-aminoph
Enyl) -6,6'-bibenzoxazole 115.5
g (0.276 mol), trimellitic acid anhydride
De [tris (methaculoyl) pentaerythritol]
11.3 g (0.022 mol) of ester and N, N-
Ice-cooled stirring of 1104 g of dimethylacrylamide homogeneous solution
Under stirring, 3,3 ', 4,4'-benzophene
42.6 g of non-tetracarboxylic anhydride (0.132 mol
) And 28.8 g of viromellitic dianhydride (0.132)
Mol) was added as a powder in small portions. Then ice cold
The reaction was carried out at room temperature for 3 hours and at room temperature for 20 hours. The obtained po
666.7 parts of riamic acid (100 parts solids), B
2 parts of TTB (λmax = 340 nm) and N-phenyl
Two parts of lysine were added and dissolved at room temperature. From this one
The residual stress of the obtained film was measured. <Residual Stress Measurement Method and Results>
Using the compositions obtained in Examples 2-3 and Comparative Example 4,
And measured. Sets obtained in Examples 2-3 and Comparative Example 4
The product was placed on a silicon wafer (crystal
Orientation 100), applied and dried in the same manner as in Example 2, and
750mJ / cm at A-501F ^Two Exposure energy
Exposed at 400 ° C. for 2 hours in a nitrogen gas atmosphere.
After imidization under heat treatment conditions, warpage of the wafer
With a stylus type surface profiler P-10 (manufactured by Tencor)
The P-10 built-in was measured from the measured value and the film thickness after imidization.
It was obtained by calculation using a residual stress calculation program. The result is displayed
It is shown in FIG. [Table 1] Use as little photosensitizing agent as possible
Use a photosensitizer that is easily removed (easy to disassemble and remove)
The composition of Example 3 used had the lowest residual stress. According to the present invention, resist characteristics such as sensitivity can be improved.
Excellent stability, good storage stability, and low residual stress of the film
A photosensitive polyimide resin composition can be provided.
The photosensitive polyimide resin composition of the present invention is used for a semiconductor device.
It is useful as a surface protective film, an interlayer insulating film, and the like. Also book
The photosensitive polyimide resin composition of the present invention is used for the interlayer of a multilayer circuit.
Cover coat, solder for insulating film and flexible copper clad board
Also used as resist film or liquid crystal alignment film
Can be

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kei Sakamoto 1-2-1, Yasuko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Within Zeon Corporation (72) Inventor Yasuhiro Yoneda 1015 Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Fujitsu Inside (72) Inventor Takao Yokouchi 1015 Uedanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fujitsu Co., Ltd. (72) Inventor Daisuke Mizutani 1015 Ueodanaka, Nakahara-ku, Nakasaki-ku, Kawasaki, Kanagawa Prefecture Inside Fujitsu Co., Ltd. (72) Person Yoshikatsu Ishizuki 1015 Ueodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Inside Fujitsu Limited (56) References JP-A-5-86154 (JP, A) JP-A-6-16520 (JP, A) JP-A-6 -102667 (JP, A) JP-A-4-77741 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) Claims: (A) A polyamic acid compound represented by the general formula (1): [Wherein, R ¹ is a tetravalent organic group, and R ² is a divalent organic group. k is an integer of 5 to 10,000.
Z is an actinic radiation functional group represented by the following formula (2). Embedded image (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are substituents having a photopolymerizable carbon-carbon double bond.
Or 1. A photosensitive resin composition comprising: (B) a photosensitive auxiliary having a photopolymerizable functional group; and (C) a solvent.