JP2993128B2 - Method for producing photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyimide precursor solution having a functional group and a method for producing a photosensitive resin composition.

[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, but has various problems. For example, JP
JP-A-145794 discloses a compound containing a double bond and an amino group or a quaternary salt thereof. However, since this compound is prepared by adding a compound containing a large amount of an amino group or a quaternized salt thereof to an unstable polyamic acid solution, there is a drawback that the viscosity of the solution greatly changes with time. Also, a method of reacting a polyamic acid with an unsaturated epoxy compound or an isocyanate compound having a double bond is disclosed (JP-A-55-45746, JP-A-60-1).
00143). However, these methods have a disadvantage that the viscosity of the solution changes due to the decomposition of a part of the polyamic acid during the reaction. Further, Japanese Patent Publication No. 55-41422 discloses a reaction for producing a polymer in which a photosensitive group such as a double bond is introduced into an ester side chain of a polyamic acid. In this reaction, chloride is produced as a by-product. Compound removal is problematic. Japanese Patent Application Laid-Open No. 61-2554547 discloses a method of synthesizing a polyisoimide and attaching a functional group thereto. This method discloses the use of N, N'-dihydrocarbyl-substituted carbodiimides such as dicyclohexylcarbodiimide and halogenated lower fatty acid anhydrides such as trifluoroacetic anhydride as dehydrating agents. However, when such a dehydrating agent is used, a disadvantage is that a purification step is required because a precipitate is formed as a by-product and unreacted reagents need to be removed.

[0003]

The problem to be solved by the present invention is to remedy the above-mentioned disadvantages of the prior art. That is, an object of the present invention is to provide a production method for easily obtaining a photosensitive resin composition having good storage stability by a one-pot method without requiring a purification step from a polyamic acid solution, and to provide a functional base which is a base of the composition. An object of the present invention is to provide a method for producing a polyimide precursor solution having a group.

[0004]

Means for Solving the Problems As a result of repeated studies on the above-mentioned problems, the present inventors have found that a dihydroquinoline derivative and a compound having a functional group such as a double bond are added to an organic solvent solution of polyamic acid. By reacting, a polyimide precursor solution was successfully obtained, and further studies were carried out to complete a method for producing a polyimide precursor solution having a functional group and a method for producing a photosensitive resin composition according to the present invention.

The method for producing a polyimide precursor solution having a functional group according to the present invention comprises the steps of: adding a dihydroquinoline derivative represented by the following formula (I) to a solution of a polyamic acid in an organic solvent;
And reacting by adding at least one of the compounds represented by the formula (III).

Embedded image R ³ —NH—R ⁴ (II) R ⁵ —OH (III) (wherein, in the formulas (I), (II) and (III), R ¹ and R ² each independently have 1 to 1 carbon atoms) 8, a monovalent organic group, R ³ is a monovalent organic group containing at least one of an unsaturated double bond, a hydroxyphenyl group and a thiol group, and R ⁴ is an unsaturated double bond, a hydroxyphenyl group, a thiol group Represents a monovalent organic group containing at least one of the following, a monovalent organic group other than that, or a hydrogen atom.)

The method for producing the photosensitive resin composition of the present invention comprises adding one or more of a photosensitive agent, a sensitizer, and a photopolymerization initiator to a polyimide precursor solution having a functional group obtained by the above-mentioned method. It consists of doing.

The polyamic acid used in the production method of the present invention is
formula

Embedded image

(Where R ⁶ is a tetravalent organic group;
⁷ is a divalent organic group, and n is a positive integer. ) Is a compound soluble in an organic solvent. Polyamic acid is usually obtained by reacting tetocalarbonic dianhydride with a diamine in an organic solvent. This reaction solution is
It can be used as a polyamic acid organic solvent solution in the production method of the present invention.

The dihydroquinoline derivative used in the production method of the present invention is represented by the formula (I). Specific examples include N-methoxycarbonyl-2-methoxy-1,2-dihydroquinoline and N-methoxycarbonyl-2-ethoxy-1,2-
Dihydroquinoline, N-ethoxycarbonyl-2-methoxy-1,2-dihydroquinoline, N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, N-
Propoxycarbonyl-2-propoxy-1,2-dihydroquinoline, N-isobutoxycarbonyl-2-methoxy-1,2-dihydroquinoline, N-isobutoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
N-isobutoxycarbonyl-2-isobutoxy-1,
2-dihydroquinoline, N-pentoxycarbonyl-2
-Pentoxy-1,2-dihydroquinoline and the like, but are not necessarily limited thereto.

Specific examples of R ³ of the compound represented by formula (II) used in the production method of the present invention are shown below, but are not limited thereto.

As the group having an unsaturated double bond,

Embedded image And so on.

The organic group containing a thiol group includes

Embedded image Can be given.

[0013] Examples of the organic group containing a hydroxyalkyl group include:

Embedded image Can be given.

R ⁴ of the compound represented by the formula (II) is
Any one of ³ or a hydrogen atom or another monovalent organic group.

Specific examples of R ⁵ of the compound represented by the formula (III) used in the production of the present invention include a monovalent organic group having an unsaturated double bond represented by the formula (6) or a hydroxy group represented by the formula (8) It is a monovalent organic group containing a phenyl group.

As a preferred solvent (hereinafter sometimes referred to as a reaction solvent) for obtaining a polyamic acid by the reaction of tetracarboxylic dianhydride with diamine in the production method of the present invention, 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, cyclohexanone, cresol, γ-butyrolactone, isophorone, N, N, -diethylacetamide, N, N-
Diethylformamide, N, N-dimethylmethoxyacetamide, tetrahydrofuran, N-acetyl-2-pyrrolidone, N-methyl-ε-caprolactam, tetrahydrothiophene dioxide persulfolane (sulpholan
e) I can raise｝. This reaction can also be performed in a mixed solvent obtained by mixing the above organic solvents. Furthermore, the preferred organic solvents described above may be replaced with other aprotic (neutral) organic solvents such as aromatic, alicyclic or aliphatic hydrocarbons, or their chlorinated derivatives (eg, benzene, toluene, xylenes). , Cyclohexane, pentane, hexane, petroleum ether, methylene chloride) or dioxane.

A method for producing a polyimide precursor solution having a functional group according to the present invention will be described.

By reacting the tetracarboxylic dianhydride with the diamine in an organic solvent, the polyamic acid represented by the above formula (IV) is obtained. The solution of the formula (I)
By adding a dihydroquinoline derivative represented by the following formula, a polyisoimide represented by the following formula (V) can be obtained.
The reaction formula is shown below.

Embedded image (Here, R ¹ , R ² , R ⁶ and R ⁷ are the same as described above.)

The carbon dioxide produced as a by-product is removed as a gas outside the system, and the alcohol and quinoline are dissolved in the solvent, and need not be removed again. The reaction temperature is 0-100 ° C, preferably 10-50 ° C. The amount of the dihydroquinoline derivative added to the polyamic acid can be theoretically converted to polyisoimide by adding two molecules of the dihydroquinoline derivative to one amic acid repeating unit. . However, there is no particular problem even if the hydroquinoline derivative is added in excess, and the amount may be small. However, when the amount is small, a polymer in which isoimide repeating units and amic acid repeating units coexist is obtained. Hydroquinoline derivative 0.2 to 2 per amic acid repeating unit
0 molecules, preferably 1 to 10 molecules, more preferably 1.
It is desirable to add 5 to 4 molecules. Also, depending on the reaction conditions, the formed isoimide may be partially converted to imide, and a polymer containing imide, isoimide, and amide acid repeating units may be formed.

Further, when polyamic acid is obtained by the reaction of tetracarboxylic dianhydride with diamine, a terminal is terminated with a monofunctional anhydride such as phthalic anhydride or a monofunctional amine such as aniline or aminopropyltriethoxysilane. Can be similarly exchanged for polyisoimide.

At least one compound represented by the formula (II) or the formula (III) is added to the solution of the polyisoimide obtained by the above reaction, and the mixture is reacted to obtain a compound represented by the following formula (V)
A polyimide precursor having a functional group containing a repeating unit represented by I) or formula (VII) can be obtained.

Embedded image

Embedded image (However, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above)

As described above, first, a solution of a polyisoimide is formed, and the compound represented by the formula (II) or (III) is reacted with the solution to produce the polyimide precursor solution of the present invention. A method in which a compound represented by the formula (II) or (III) is mixed in advance with a dihydroquinoline derivative and then the mixture is added to a polyamic acid, or the compound represented by the formula (II) or (III) A method is also possible in which after mixing with a polyamic acid, a dihydroquinoline derivative is added to the mixture to carry out the reaction.

When the compounds having the functional groups represented by the formulas (II) and (III) are simultaneously added and reacted,
A polymer having the repeating units represented by the formulas (VI) and (VII) simultaneously in one molecule can be obtained.

However, alcohol is by-produced (R ¹ OH, R ² O) by the polyamic acid and the dihydroquinoline derivative in the step shown in Chemical formula 9 for producing a polyisoimide.
H). This alcohol may also add to the isoimide. However, in the case of the compound (II), the addition reaction occurs earlier than the alcohol, so that the compound (II) is not much affected by the by-product alcohol. In the case of the compound of the formula (III), a competitive reaction occurs with the by-product alcohol. In such a case, the effect of the by-product alcohol can be reduced by adding the compound of the formula (III) in a larger amount than the by-product alcohol.

The logarithmic viscosity number of the functional group-containing polyimide precursor according to the production method of the present invention is preferably in the range of 0.1 to 5 dl / g from the viewpoint of film-forming properties. Here, the logarithmic viscosity number is η _inh represented by the following equation. η _inh = (In η / η ₀ ) / C (where η _inh is a Ubbelohde viscometer, and a solution having a polymer concentration of 0.5 g / dl in a solvent is heated to a temperature of 30 ± 0.0.
Is the viscosity measured at 1 ° C., η ₀ is the viscosity of the same solvent at the same temperature using the same viscometer, and C is the concentration of 0.
5 g / dl).

Formula (VI) or Formula (VII) in a polyimide precursor
The more repeating units having the functional group represented by the formula, the more preferable, but it is not necessary to be 100%. However, practically, it is preferable that it be present at 5% or more. Formula (VI) or Formula (VI
It is not necessary to particularly limit the repeating unit other than (I), but according to the production method of the present invention, one or other unreacted isoimide, amide acid, imide or amide ester to which by-product alcohol is added is included. Could be

In the production method of the present invention, the compound represented by the formula (II) or (I
The total amount of the compound represented by the formula (II) may be not less than or more than equimolar to the dihydroquinoline derivative, but is preferably about equimolar to about 5-fold molar. Reaction time is 0 to 100 ° C,
Preferably it is about 10 to 50 ° C. The reaction time is 0.
It is about 2 to 100 hours, preferably about 5 to 50 hours.

The polyamic acid in the production method of the present invention can be obtained by reacting an anhydride of a tetracarboxylic acid with a diamine. The following compounds can be mentioned as the tetracarboxylic dianhydride, but the present invention is not limited thereto. Not something.

As the aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3
3'-biphenyltetracarboxylic dianhydride, 2,3
3 ', 4'-biphenyltetracarboxylic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid Dianhydride, bis (3,4-dicarboxyphenyl) -ether dianhydride, bis (3,4-
Dicarboxyphenyl) -sulfone dianhydride, 1,2,2
5,6-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
Examples of alicyclic tetracarboxylic dianhydrides such as 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride include cyclobutanetetracarboxylic dianhydride and methylcyclobutanetetracarboxylic dianhydride Such as aliphatic tetracarboxylic dianhydride, 1,
2,3,4-tetracarboxybutane dianhydride and the like can be mentioned.

Examples of the diamine include, but are not necessarily limited to, the following compounds.
As aromatic diamines, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-di (meth-aminophenoxy) diphenylsulfone, 4,4'-di (Para-aminophenoxy) diphenyl sulfone, ortho-phenylenediamine, meta-phenylenediamine, para-phenylenediamine, benzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4 '
-Diaminodiphenyl-2,2'-propane, 1,5-
Diaminonaphthalene, 1,8-diaminonaphthalene,
3,4'-diaminodiphenyl ether, 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, 1,3-bis (3-aminophenoxy) benzene,
4,4'-diamino-3,3'-cyethyl-5,5'-
Dimethyldiphenylmethane, 4,4'-diamino-3
3 '-, 5,5'-tetramethyldiphenylmethane,
Aliphatic diamines such as 1,4-diaminotoluene, meta-xylylenediamine and 2,2'-dimethylbenzidine include trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4-dimethylheptamethylenediamine, Silicon-based diamines such as 1,11-dodecanediamine, bis (p-aminophenoxy) dimethylsilane and 1,4-bis (3-aminopropyldimethylsilyl) benzene; alicyclic diamines such as 1,4- Examples of guanamines such as diaminocyclohexane, bis (4-aminocyclohexyl) methane, and isophoronediamine include acetoguanamine and benzoguanamine.

The following compounds can be mentioned as diaminopolysiloxanes.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

Embedded image (However, the above p is 1 to 100.)

The method for producing the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention is obtained by adding at least one of a photosensitizer, a sensitizer, and a photopolymerization initiator to the polyimide precursor solution having a functional group obtained as described above. Can be

The photosensitizer is preferably a diazide compound, and specific examples thereof include 2,6-di (p-azidobenzal) -4-methylcyclohexanone and 2,6-di (p-
Azidobenzal) cyclohexanone, 4,4'-diazidochalcone, 4,4'-diazidobenzalacetone,
4,4'-diazidostilbene, 4,4'-diazidobenzophenone, 4,4'-diazidophenylmethane,
4,4'-diazidophenylamine and the like can be mentioned. However, it is not necessarily limited to these.

The amount of the photosensitive agent to be added is from 0 to 50% by weight, preferably from 1 to 20% by weight, based on the functional group-containing polyimide precursor.
% By weight.

Specific examples of the sensitizer or photopolymerization initiator include benzoin, benzoin ether, benzophenone, p, p'-dimethylbenzophenone, 4,4'-bis- (diethylaminobenzophenone), Michler's ketone, and 2-nitrofluorene. 5,5-nitroacenaphthene, 4-nitro-1-naphthylamine, anthrone,
1,9-benzoanthrone, dibenzalacetone, anthraquinone, 2-methylanthraquinone, 1-nitropyrene, 1,8-dinitropyrene, pyrene-1,6-quinone, cyanoacridine, benzoquinone, 1,2-naphthoquinone, , 4-naphthoquinone, 1,2-benzanthraquinone and the like. However, the invention is not necessarily limited to these.

The addition amount of the sensitizer or photopolymerization initiator is from 0 to 20 with respect to the polyimide precursor each having a functional group.
% By weight, preferably 0 to 10% by weight. The total amount of the photosensitizer, sensitizer and photopolymerization initiator is 0.1 to 50% by weight.

Further, if necessary, a compound having a carbon-carbon double bond of 20% by weight or less or a polyvalent thiol may be added as a crosslinking aid to the polyimide precursor. Specific examples include butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, benzyl acrylate, carbitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate,
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, N-methylol acrylamide, N
-Diacetone acrylamide, N, N'-methylenebisacrylamide, N-vinylpyrrolidone, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, neo Pentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4
-Butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate,
Examples thereof include pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetra (3-mercaptopropionate), and pentaerythritol tetra (mercaptoacetate).

In some cases, a polymerization inhibitor such as hydroquinone or p-methoxyphenol or an auxiliary material such as a dye or pigment may be added.

As described above, according to the production method of the present invention, a polyisoimide precursor having a functional group introduced therein is produced following the synthesis of polyamic acid and the synthesis of polyisoimide. All of the steps of producing the photosensitive resin composition of the present invention by adding a polymerization initiator can be performed by a one-pot method.

Next, a method for forming a patterned polyimide film using the polymer solution or the photosensitive resin composition obtained by the production method of the present invention will be described. The polymer solution or the photosensitive resin 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 at 30 to 150 ° C using a heating means such as an electric furnace or a hot plate.
Most of the solvent in the coating film is removed by performing prebaking for several minutes to several tens of minutes at the above temperature. A negative mask is placed on the coating film and irradiated with actinic radiation. X for actinic radiation
Examples include rays, electron beams, ultraviolet rays, far ultraviolet rays or visible light rays, and ultraviolet rays or far ultraviolet rays are particularly preferred. Next, a relief pattern is obtained by dissolving and removing the unexposed portion with a developing solution. The developer can be selected from the reaction solvents, and a mixture of the developer and a lower alcohol such as methanol, ethanol or propanol which is a non-solvent of the photosensitive polymer of the present invention can also be used.

The relief pattern can be stabilized by rinsing in the above-mentioned non-solvent if necessary, and further drying at a temperature of 150 ° C. or less. 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, the polymer is heated at a temperature of 200 to 500 ° C., preferably 300 to 400 ° C. for several tens minutes to several hours by the above-mentioned heating means. A modified polyimide film is formed. The chemical reaction in this case is as shown below.
The photosensitive component volatilizes by thermal decomposition to form a polyimide.

[0051]

Embedded image (However, R ⁴ , R ⁶ and R ⁷ are as described above. Q represents a component containing a crosslinked functional group). Thus, a patterned heat-resistant polyimide film can be obtained from the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention can be applied to electronic materials, particularly to passivation films for semiconductors, printed circuits and the like.

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 A 1-liter flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser, and a nitrogen purge device was fixed in cold water. After the atmosphere in the flask was replaced with nitrogen gas, 500 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) dehydrated and purified,
21.92 g of 4'-diaminodiphenyl ether
(0.109 mol) and 35.28 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
(0.109 mol) was added to obtain a polyamic acid solution according to a conventional method. Add N-ethoxycarbonyl-2 to this solution.
-Ethoxy-1,2-dihydroquinoline (hereinafter referred to as EEDQ
) Was added, and the reaction was carried out at 10 to 20 ° C for 3 hours to generate violent carbon dioxide gas. 16.91 g (0.174 mol) of diallylamine was added to this solution, and 20
The solution was reacted at ３０30 ° C. for 5 hours to obtain a solution containing a polyimide precursor having a functional group (logarithmic viscosity number: 1.35 dl / g). Furthermore, 2,6-di (p-azidobenzal) -4-
1.60 g of methylcyclohexanone (hereinafter abbreviated as bisazide-1) and 1.03 of Michler's ketone
g was added and dissolved to obtain a photosensitive resin composition of the present invention.

Example 2 Using the same apparatus and method as in Example 1, 500 g of 500 g of N, N-dimethylacetamide (abbreviated as DMAC) and 13.89 g of 3,3'-diaminodiphenyl sulfone (0. 0.0559 mol) and 18.02 g (0.0559 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
Were mixed to obtain a polyamic acid solution according to a conventional method. 27.65 g (0.112 mol) of EEDQ and p
12.21 g (0.112 mol) of aminophenol
Was added, and the mixture was reacted at 20 to 30 ° C. for 10 hours to obtain a solution containing a polyimide precursor having a functional group having a logarithmic viscosity number of 0.51 dl / g. 2,6-
1.60 of di (p-azidobenzal) cyclohexanone
g and 0.85 g of benzuanthrone were added and dissolved to obtain a photosensitive resin composition of the present invention.

Example 3 Using the same apparatus and method as in Example 1, 500 g of dimethyl carbitol, 3,
25.11 g (0.0779 mol) of 3'4,4'-benzophenonetetracarboxylic dianhydride and 15.48 g (0.062 mol) of 3,3'-diaminodiphenyl sulfone
3 mol) and ω-ω'-bis- (3-aminopropyl) polydimethylsiloxane (molecular weight 960).
96 g (0.0159 mol) were mixed to obtain a polyamic acid solution according to a conventional method. To this solution was added 34.6 of EEDQ.
8 g (0.140 mol) are added,
After reacting for hours, 13.60 g of diallylamine
(0.140 mol) was added thereto, and the reaction was further performed for 5 hours to obtain a solution containing a polyimide precursor having a functional group having a logarithmic viscosity number of 0.48 dl / g. 2.78 g of pentaerythritol tetra (3-mercaptopropionate) (hereinafter abbreviated as thiol-1) was added to this solution,
3,3-, 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (hereinafter abbreviated as BTTB)
2.22 g of p-methoxyphenol and 0.12 of p-methoxyphenol
1 g was added and dissolved to obtain a photosensitive resin composition of the present invention.

Example 4 Using the same apparatus and method as in Example 1, 500 g of dimethyl carbitol and 47.94 g (0.108 mol) of hexafluoroisopropylidene-2,2-bis (phthalic anhydride) And 2,2-
40.30 g (0.0982 mol) of bis [4- (4-aminophenoxy) phenyl] hexafluoropropane was mixed to obtain a polyamic acid solution according to a conventional method. 20.01 g (0.206 mol) of diallylamine was added to this solution.
Was added in advance, and 46.14 g of EEDQ was added.
(0.187 mol) and reacted at 20-30 ° C. for 20 hours to give a logarithmic viscosity number of 0.41 dl /
Thus, a solution containing a polyimide precursor having a functional group was obtained. To this solution, 4.41 g of thiol-1 and BTTB were added.
3.53 g of p-methoxyphenol and 0.18 of p-methoxyphenol
g was added and dissolved to obtain a photosensitive resin composition of the present invention.

Example 5 By the same apparatus and method as in Example 1, 500 g of DMAC, 52.76 g (0.264 mol) of 4,4'-diaminodiphenyl ether, and 53.76 g of pyromellitic dianhydride were obtained. 88g (0.2
47 mol) and 4.89 g (0.03 g) of phthalic anhydride.
3 mol) to obtain a polyamic acid solution according to a conventional method. 73.30 g (0.296 mol) of EEDQ and 115.2-hydroxyethyl methacrylate were added to this solution.
A mixture with 44 g (0.888 mol) was added and 25-
The solution was reacted at 35 ° C. for 40 hours to obtain a solution containing a polyimide precursor having a functional group having a logarithmic viscosity number of 0.75 dl / g. 4.46 BTTB was added to this solution.
g, 2.23 g of Michler's ketone, 0.22 g of p-methoxyphenol and 3.34 g of trimethylolpropane trimethacrylate were added and dissolved to obtain a photosensitive resin composition of the present invention.

(Example 6) Using the same apparatus and method as in Example 1, 500 g of NMP and 15.78 g (0.14 g) of NMP
15.78 g of p-phenylenediamine
(0.146 mol), 1.94 g (0.02 g) of aniline
08 mol), and 50.35 g (0.15 g) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride.
6 mol), and a polyamic acid solution was obtained according to a conventional method. 75.68 g of N-isobutoxycarbonyl-2-isobutoxy-1,2-dihydroquinoline was added to this solution.
(0.250 mol) and reacted at 10-20 ° C. for 2 hours, and then 9.64 g of aminoethanethiol.
(0.125 mol) and 12.15 of diallylamine
g (0.125 mol) was added, and the reaction was further continued for 10 hours. As a result, a solution containing a polyimide precursor having a functional group having a logarithmic viscosity number of 0.82 dl / g was obtained. To this solution, 2.38 g of BTTB and 0.14 g of 0.14 g of p-methoxyphenol were added and dissolved to obtain a photosensitive resin composition of the present invention.

Example 7 Using the same apparatus and method as in Example 1, 500 g of NMP, 93.24 g (0.301 mol) of 4,4'-oxydiphthalic anhydride, and 6.55 g of maleic anhydride (0.0668 mol), and 66.86 g of 4,4'-diaminodiphenyl ether
(0.334 mol), and a polyamic acid solution was obtained according to a conventional method. 165.5 g (0.602 mol) of N-isobutoxycarbonyl-2-ethoxy-
165.5 g of 1,2-dihydroquinoline (0.602
Mol), and 58.49 g of diallylamine are added, and the mixture is added at 20 to 30 hours for 2 hours, and further at 40 to 50 ° C for 3 hours.
By performing the reaction for a time, the logarithmic viscosity number is 0.47 d.
A solution containing a 1 / g functional group-containing polyimide precursor was obtained. 8.33 g of bisazito-1 and 2
5.00 g of -nitrofluorene was added and dissolved to obtain a photosensitive resin composition of the present invention.

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 at 70 ° C. for 40 minutes to obtain a film thickness of about 3 μm. A uniform film was formed. At this time, the film thickness was adjusted by spinning the spinner and diluting the varnish with a solvent. Next, exposure was performed by irradiating with an ultra-high pressure mercury lamp (20 mW / cm ² ) for 15 seconds through a mask. This was developed by immersing it in a mixed solution of NMP and ethyl alcohol (volume ratio: 4: 1), rinsed in ethyl alcohol, and dried. Thus, a clear relief pattern was obtained. This was fired in an electric furnace at 200 ° C. for 30 minutes and further at 350 ° C. for 1 hour to obtain a patterned polyimide film. The final film thickness of the unexposed portion was measured and is shown in Table 1. Further, in order to examine the storage stability of the varnish, each varnish was stored in a refrigerator at 4 ° C., and after one month, patterning was performed by the same operation. As a result, clear relief patterns were all obtained. Further, the final film thickness of the unexposed portion after firing was measured in the same manner, and the results are shown in Table 1. As is apparent from this, it is clear that the photosensitive resin composition of the present invention has practically sufficient sensitivity and storage stability.

[Table 1]

[0062]

Industrial Applicability The production method of the present invention provides a method for introducing a functional group into a polyamic acid by a one-pot method without requiring a purification step, and provides a polyimide precursor having a functional group obtained with a photosensitive agent or the like. Thus, a photosensitive resin composition can be easily obtained simply by adding the additive. Furthermore, the photosensitive resin composition obtained by the production method of the present invention has practically sufficient sensitivity and storage stability, and has great industrial effects.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 73/10 C08L 79/08 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A polyamic acid solution in an organic solvent,
A method for producing a polyimide precursor solution having a functional group, comprising reacting a dihydroquinoline derivative represented by the formula (I) with at least one of the compounds represented by the following formulas (II) and (III): . Embedded image R ³ —NH—R ⁴ (II) R ⁵ —OH (III) (In the formulas (I), (II) and (III), R ¹ and R ² each independently have 1 to 8 carbon atoms.) R ³ is a monovalent organic group containing at least one of an unsaturated double bond, a hydroxyphenyl group and a thiol group, and R ⁴ is an unsaturated double bond, a hydroxyphenyl group and a thiol group Represents a monovalent organic group containing at least one of the following, a monovalent organic group other than that, or a hydrogen atom.) 2. The method for producing a polymer solution according to claim 1, wherein the polyamic acid organic solvent solution is a solution obtained by reacting tetracarboxylic dianhydride and diamine in an organic solvent. 3. A polyimide precursor solution having a functional group is a solution of a polymer having a repeating unit represented by the formula (VI) or (VII), or a repeating unit represented by the formulas (VI) and (VII). 3. The method for producing a polyimide precursor solution according to claim 1, wherein the solution is a solution of a polymer simultaneously containing Embedded image Embedded image (However, R ³ is a monovalent organic group containing at least one of an unsaturated double bond, a hydroxyphenyl group and a thiol group,
R ⁴ represents a monovalent organic group containing at least one of an unsaturated double bond, a hydroxyphenyl group and a thiol group, or a hydrogen atom. R ⁶ is a tetravalent organic group, and R ⁷ is a divalent organic group. ) 4. A photosensitive resin composition obtained by adding at least one of a photosensitizer, a sensitizer and a photopolymerization initiator to a polyimide precursor solution having a functional group obtained by the production method according to claim 1. Manufacturing method. 5. A photosensitive resin composition obtained by adding at least one of a photosensitive agent, a sensitizer and a photopolymerization initiator to a polyimide precursor solution having a functional group obtained by the production method according to claim 2. Manufacturing method. 6. A photosensitive resin composition obtained by adding one or more of a photosensitive agent, a sensitizer and a photopolymerization initiator to a polyimide precursor solution having a functional group obtained by the production method according to claim 3. Manufacturing method.