JPH0678485B2 - Photosensitive polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive polymer composition used in electronic devices such as semiconductor devices.

(Prior Art) Conventionally, as a surface protective film or interlayer insulating film for semiconductor elements, film formation is easy, planarization is possible, heat resistance is high, and electrical and mechanical properties are excellent. For this reason, polyimide is widely used.

In addition, recently, many studies have been conducted on the development of a photosensitive polymer composition that also functions as a photoresist for the purpose of streamlining the film forming process using polyimide.
As one example, a method is known in which a polyamic acid, which is a polyimide precursor, is used as a base polymer, and a bisazide compound and an amine compound having a carbon-carbon double bond are added.

This composition is applied to a substrate in a solution state and dried, and after forming a coating film, it is exposed by using a predetermined mask, a pattern is formed by development, and then cured at a temperature of 200 to 400 ° C. Although used as a polyimide, the properties of the solution state and the final cured film are greatly affected by the polyamic acid used as the base.

The polyamic acid used here can be generally obtained by reacting a diamine and a tetracarboxylic dianhydride in an organic solvent, and the polyimide obtained after curing has excellent heat resistance up to the present Many are known to have excellent properties and excellent solubility. For example 4,
Polyamic acid having a structural unit represented by the formula [I] obtained from 4'-diaminodiphenyl ether and pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 3,3 ', 4,4'- When a polyamic acid having a structural unit represented by the formula [II] obtained from biphenyltetracarboxylic dianhydride is used as a base polymer, Although it has excellent flexibility and heat resistance, it is difficult to prepare a high-concentration and low-viscosity solution because it has poor solubility in a solvent. There was a drawback that the solution stability of the combined composition was poor.

Next, in order to improve the solubility of the polyamic acid, 4,
When a polyamic acid having a structural unit represented by the formula [III] obtained from 4'-diaminodiphenyl ether and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride is used as a base polymer The main chain is benzene, which has excellent flexibility. Since a carbonyl group that is easily cleaved by heat is contained between the ring and the benzene ring, the heat resistance of the final cured film of the photosensitive polymer composition using this has a drawback.

(Problems to be Solved by the Invention) The present invention provides a photosensitive polymer composition at a high concentration in a solution state which cannot be obtained by the above-described conventionally known polyamic acid or a combination thereof. And low viscosity,
It was obtained as a result of diligent studies on a polyamic acid having good viscosity stability and also properties such as heat resistance and flexibility when used as a final cured film.

(Means for Solving Problems) The present invention relates to a photosensitive polymer composition containing a polyamic acid, a bisazide compound, and an amine compound having a carbon-carbon double bond, and meta-terphenyl as an acid component as polyamic acid. The present invention relates to a photosensitive polymer composition using a polyamic acid obtained by using -3,4,3 ", 4" -tetracarboxylic dianhydride.

The polyamic acid used in the present invention has, for example, a structural unit represented by the formula [IV].

(However, in the formula, R ′ represents a divalent organic group, and the positional relationship between the amide group and the carboxyl group is not limited to this formula, and the positions of the amide group and the carboxyl group may be reversed.) The novel polyamic acid used as the base polymer is a novel meta-terphenyl-3,4,3 ", 4" -tetracarboxylic dianhydride represented by the following formula [V]. It is obtained by reacting a diamine with a diamine in an organic solvent.

This acid anhydride is a novel compound obtained by the present inventors and is obtained by a double cross coupling reaction represented by the formula [IV] shown below.

(However, in the formula, X ₁ X ₂ represents chlorine, bromine, or iodine.) Meta-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic dianhydride is 4-bromo-orthoxylene. After reacting with metallic magnesium to form Grignard reagent, it was subjected to double cross-coupling reaction with metadihalogenobenzene in the presence of nickel metal complex catalyst such as dichlorobis (triphenylphosphine) nickel and dibromobis (triphenylphosphine) nickel. Tetramethyl-
Meta-turfenyl. Next, this is converted to meta-terphenyl tetracarboxylic acid by permanganate, nitric acid, liquid-phase air oxidation, and then heated or acetic anhydride is added to meta-terphenyl tetracarboxylic acid dianhydride. It can be a thing.

Moreover, when obtaining a polyamic acid, you may use together other tetracarboxylic acid dianhydride. For example, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, cyclopentanetetracarboxylic acid Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6
-Pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic acid A dianhydride or the like is used.

When other tetracarboxylic dianhydrides are used,
The polyamic acid will contain structural units different from the above structural units.

The diamine component used in the present invention includes, for example, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfide, benzine, meta-phenylenediamine, para-phenylenediamine,
Aromatic diamines such as 1,5-naphthalenediamine and 2,6-naphthalenediamine are used.

In addition to this, the following general formula [VII] (Wherein R ² is a divalent hydrocarbon group, R ³ is a monovalent hydrocarbon group, R ² and R ³ may be the same or different, and m is an integer of 1 or more) Diaminosiloxane can be used as this compound And so on.

General formula [VIII] (However, Ar represents an aromatic group, Y represents SO ₂ or CO, and one amino group and Y—NH ₂ are located in the ortho positions with respect to each other.) A diaminoamide compound can also be used. This compound includes 4,4'-diaminodiphenyl ether-
3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide , 4,4'-Diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfonamide, 3,3 ′ -Diaminodiphenylmethane-4-sulfonamide, 4,4′-
Diaminodiphenyl sulfone-3-sulfonamide, 3,
4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diamino Diphenyl sulfide-3-sulfonamide, 3,4'-diaminodiphenyl sulfide-4-sulfonamide, 3,3'-diaminodiphenyl sulfide-4-sulfonamide, 3,4'-diaminodiphenyl Sulfaid-3'-sulfonamide, 1,4
-Diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-
Diaminodiphenyl ether-4-carbonamide, 3,
4'-diaminodiphenyl ether-3'-carbonamide, 3,3'-diaminodiphenyl ether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diamino Diphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3 '
-Carboxamide, 3,3'-diaminodiphenylmethane-
4-carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide , 3,3'-Diaminodiphenylsulfone-4-carboxamide, 4,4'-diaminodiphenyl sulfide-3-carbonamide, 3,4 '
-Diaminodiphenyl sulfide-4-carbonamide, 3,3'-diaminodiphenyl sulfide-4-carbonamide, 3,4'-diaminodiphenyl sulfide-
3'-sulfonamide, 1,4-diaminobenzene-2-carbonamide and the like can be mentioned.

In addition, the general formula [IX] (Wherein Ar represents an aromatic group, Y represents SO ₂ or CO, and one amino group and one Y-NH ₂ group are positioned in the ortho position with respect to each other) This compound can be used as 4,4'-diaminodiphenyl ether-3,3'-sulfonamide, 3,4'-diaminodiphenyl ether-4,5'-carbonamide, 3,3 '
-Diaminodiphenyl ether-4,4'-sulfonamide, 4,4'-diaminodiphenylmethane-3,3'-carbonamide, 3,4'-diaminodiphenylmethane-4,5'-
Examples include sulfonamide.

The polyamic acid in the present invention is, for example, N-methyl-2.
-Dissolve the diamine component in a polar solvent such as pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylenephosphoramide, tetramethylenesulfone, p-chlorophenol, p-bromophenol. After that, meta-turfenyl-3,
It can be obtained by adding 4,3 ″, 4 ″ -tetracarboxylic dianhydride or an acid component containing the same, and reacting the mixture at a temperature of 80 ° C. or lower, preferably around room temperature or lower, with stirring. The acid component and the diamine component are preferably used in equimolar amounts.

The bisazide compound used in the present invention includes Etc. are mentioned as a suitable example.

From the viewpoint of storage stability of the developing varnish, the amount of the bisazide compound is preferably 0.1 to 100 parts by weight, and more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the polyamic acid.

Examples of the amine compound having a carbon-carbon double bond include 2- (N, N-dimethylamino) ethyl acrylate,
2- (N, N-dimethylamino) ethyl methacrylate, 3-
(N, N-dimethylamino) propyl acrylate, 3-
(N, N-dimethylamino) propyl methacrylate, 4-
(N, N-dimethylamino) butyl acrylate, 4- (N, N
-Dimethylamino) butyl methacrylate, 5- (N, N-
Dimethylamino) pentyl acrylate, 5- (N, N-dimethylamino) pentyl methacrylate, 6- (N, N-dimethylamino) hexyl acrylate, 6- (N, N-dimethylamino) hexyl methacrylate, 2- (N, N-dimethylamino) ethyl cinnamate, 3- (N, N-dimethylamino) propyl cinnamate, sorbitan acid 3- (N,
N-dimethylamino) propyl, sorbitan acid 2- (N, N
-Dimethylamino) ethyl, sorbitan acid 4- (N, N-
Dimethylamino) butyl and the like can be mentioned.

The blending ratio of this amine compound is 10% from the viewpoint of the developability and the film properties of the final product polyimide.
The range of 1 to 400 parts by weight relative to 0 parts by weight is preferable.

The photosensitive polymer composition of the present invention comprises the above polyamic acid,
A bisazide compound and an amine compound having a carbon-carbon double bond are dissolved in a suitable solvent to give a solution.

The organic solvent used at this time is preferably an aprotic polar solvent from the viewpoint of solubility, for example, N-methyl-2
-Pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone and the like. These organic solvents may be used alone or in combination of two or more.

The mixing ratio of the organic solvent is 1 with respect to 100 parts by weight of the mixture of the polyamic acid, the bisazide compound and the amine compound.
The amount is 00 to 10,000 parts by weight, preferably 200 to 5,000 parts by weight. If this proportion is less than 100 parts by weight, or 10,00
If it exceeds 0 parts by weight, the film-forming property is adversely affected.

The photopolymer composition according to the present invention may contain a sensitizer such as Michler's ketone, anthrone or 5-nitroazenaphthene, if necessary.

The photosensitive polymer composition of the present invention can be patterned by an ordinary fine processing technique. When the photosensitive polymer composition of the present invention is applied onto a supporting substrate such as a glass substrate or a silicon wafer, means such as spin coating using a spinner, dipping and spray printing are used. The coating film thickness can be adjusted by the coating means, the solid content concentration and viscosity of the varnish of the photosensitive polymer composition of the present invention.

A relief pattern is obtained by irradiating the photosensitive polymer composition of the present invention, which has been formed into a film, with a light source on the supporting substrate by the drying step, and then dissolving and removing the unexposed portion with a developing solution. At this time, ultraviolet light, visible light, radiation or the like is used as the light source.

As the developing solution, for example, N-methyl-2-pyrrolidone, N
-Acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone, N-benzyl-2-pyrrolidone, N-acetyl-ε-caprolactam An aprotic polar solvent such as, for example, a non-solvent of polyamic acid, eg methanol,
It is used as a mixed solution with ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, water and the like.

Next, the relief pattern formed by the development is washed with a rinse liquid to remove the developing solvent. As the rinse liquid, a non-solvent of polyamic acid having good miscibility with the developer is used, and examples thereof include methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, and water.

The relief pattern polymer obtained by the above treatment is a polyimide precursor, and by heat treatment at 150 to 450 ° C., it becomes a relief pattern of a heat resistant polymer having an imide ring or other cyclic group.

(Examples) Hereinafter, the present invention will be described with reference to Examples, Reference Examples and Comparative Examples.

Reference example Synthetic example of meta (m) -terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic acid and its anhydride (1) Production of Grignard reagent Aline condenser, dropping funnel, thermometer and stirring device are attached. 100 ml of the 2nd four-neck flask dehydrated with metallic sodium after being sufficiently dried under an argon gas atmosphere.
Tetrahydrofuran, 9.72 g of metallic magnesium and 1
0.0 g of bromo-ortho-xylene (Aldrich, 4
-Bromo-orthoxylene 75% and 3-bromo-orthoxylene 25% mixture) was added. When the reaction solution began to become muddy and the Grignard reagent started to form, a mixed solution of 64.0 g of bromo-orthoxylene and 100 ml of tetrahydrofuran was added dropwise from a dropping funnel over 1 hour. During this period, since the reaction was exothermic, the reaction temperature was kept at 40 ° C while cooling with an ice bath. Since metallic magnesium remains after the dropping, it was heated in an oil bath and stirred at a temperature of 40 ° C. for 5 hours to completely react metallic magnesium to obtain a Grignard reagent.

(2) Preparation of 3,4,3 ″, 4 ″ -tetramethyl-m-terphenyl Next, 0.37 g of the dichloro [1,2-bis (diphenylphosphino) ethane] nickel catalyst (the above-mentioned broth was added to the flask). 0.5% by weight based on the total amount of moorthoxylene),
A solution prepared by dissolving 29.4 g (0.200 mol) of meta-dichlorobenzene in 85 ml of tetrahydrofuran was added dropwise from the dropping funnel over 1 hour. During this time, the reaction temperature was kept at 35 ° C. After the completion of the dropping, stirring was continued for an additional 1 hour while maintaining the temperature at 35 ° C to complete the double cross coupling reaction.

To the reaction-terminated liquid was added 300 ml of toluene, and 150 ml of ion-exchanged water was gradually added with stirring over 1 hour. After removing the lower aqueous layer with a separating funnel, the upper toluene layer was driven up with a rotary evaporator. After cooling, the precipitated crystals were taken out, washed with ethanol three times, and dried under reduced pressure to obtain 24.4 g of colorless plate crystals. The melting point of this crystal is 72 to 73 ° C., and FIG. 1 shows the results of analysis of the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum and FIG. 2 of the carbon nuclear magnetic resonance ( ¹³ C-NMR) spectrum. Show. 2.29ppm and 2.32ppm in Figure 1
The integrated intensity ratio between the absorption based on the methyl group protons and the absorption based on the benzene ring protons of the former is 180: 150 (= 1
2:10), which is in good agreement with the theoretical value. In FIG. 2, it can be seen that the compound (theoretical carbon number 22) obtained from the fact that only 12 peaks appear has a symmetrical structure.
Moreover, the formula [XIV] The carbon number of the compound represented by ~ is in good agreement with the expected value of the chemical shift of the benzene ring carbon according to the Savitsky law of the benzene ring carbon of
10 has appeared.

From the above, the above crystals are 3,4,3 ", 4" -tetramethyl-m
-Confirmed to be terphenyl.

(3) Production of m-terphenyl, 3,4,3 ″, 4 ″ -tetracarboxylic acid 3,4,3 ″, 4 ″ -tetramethyl-meta-terphenyl, 14.3 g
(50 mmol), 200 g of pyridine and 200 g of ion-exchanged water were placed in a 1-necked flask equipped with an Aren condenser, a thermometer and a stirrer, and the inside of the flask was heated to 80 ° C., and potassium permanganate 110.7 g (700 Mmol) was gradually added over 3 hours, and then the mixture was kept at 80 ° C. for another 5 hours and stirring was continued. Precipitation of manganese oxide produced in the reaction was removed excessively, pyridine in the solution was distilled off by a rotary evaporator, and then white matter fine crystals were precipitated by acid precipitation with 36% hydrochloric acid. The pH of the solution at this time was 1. After repeating the washing with water twice, it was dried under reduced pressure to obtain 8.9 g of white powdery crystals.

The melting point of this crystal was 296 to 298 ° C. The infrared absorption spectrum of this crystal is shown in FIG. To 0.4 g of this crystal, 50 ml of methanol and 2 ml of 97% sulfuric acid were added, and the mixture was refluxed for 8 hours to methylate the above crystal. The result of ¹ H-NMR spectrum of the obtained methyl esterified product is shown in FIG. In Fig. 4, the integrated intensity ratio of the absorption based on the methyl group protons at 3.91 ppm and 3.94 ppm and the absorption based on the benzene ring protons at 7.71 to 7.95 ppm is 175: 147 (= 12: 10.08) for the former and the latter. , m-turfenyl-
It was in good agreement with the theoretical value of the methyl ester compound of 3,4,3 ", 4" -tetracarboxylic acid.

The results of elemental analysis of the above crystals are as follows.

Measured value Carbon: 59.65%, Hydrogen: 4.16% Theoretical value Carbon: 65.03%, Hydrogen: 3.47% (However, the theoretical value is m-terphenyl, 3,4,3 ″, 4 ″ −
It is a value obtained as tetracarboxylic acid. ) As a result of elemental analysis, the measured value and theoretical value are different. Therefore, when the above crystal was subjected to differential thermal balance analysis at a heating rate of 5 ° C / min, endothermic peaks were found at 211 ° C and 298 ° C. . At 211 ° C
A weight loss of 17% by weight was observed. The endothermic peak at 298 ° C is due to the melting point, while the endothermic peak at 211 ° C is due to dehydration. m-turfenyl-3,4,3 ″,
If the 4 ″ -tetracarboxylic acid only undergoes dehydration ring closure by heating during the differential thermal balance analysis to form the corresponding acid anhydride, the weight loss is 9%. Is considered to have water of crystallization, and the actual value of the above elemental analysis is based on the theory of elemental analysis when two molecules of water of crystallization are hydrated in m-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic acid. Very good agreement with the values carbon 59.73% and hydrogen 4.10%.

From the above, the above-mentioned crystal is m-turfenyl-3,4,3 ″, 4 ″
-It was confirmed that it is a tetracarboxylic acid and has two molecules of water of crystallization.

(4) Production of m-terphenyl-3,4,3 ", 4" -tetracarboxylic acid-3,4,3 ", 4" -dianhydride The obtained m-terphenyl-3,4,3 ", 8 ″ of 4 ″ -tetracarboxylic acid was placed in a 100 ml eggplant-shaped flask, the inside of the container was adjusted to 20 mmHg by a vacuum pump, and the mixture was immersed in an oil bath at 180 ° C. for 15 hours for dehydration ring closure. In this way 7.29 g of light and colored powdery crystals were obtained. The infrared absorption spectrum and ¹ H-NMR spectrum of this powdery crystal are shown in FIGS. 5 and 6, respectively.

The melting point of this crystal is 296 ~ 298 ℃, as a result of elemental analysis,
Carbon 71.17%, hydrogen 2.79%, theoretical carbon 71.36%
%, Good agreement with 2.72% hydrogen, m-terphenyl-3,4,
It was confirmed to be 3 ″, 4 ″ -tetracarboxylic acid-3,4,3 ″, 4 ″ -dianhydride.

Example 1 10 g of 4,4'-diaminodiphenyl ether under a nitrogen stream
(0.05 mol) was dissolved in 161.5 g of N-methyl-2-pyrrolidone to prepare a diamine solution.

Next, while maintaining this solution at a temperature of about 15 ° C. with ice-cooling, the solution obtained in Reference Example was stirred under stirring with meta-terphenyl-3,4,
3 ", 4" -Tetracarboxylic acid dianhydride 18.5g (0.05mol)
Was added and stirring was continued at room temperature for 8 hours to obtain a polyamic acid solution. The obtained polyamic acid solution has a nonvolatile content of 15% by weight.
The viscosity was 25 ° C and 800 poise. Next, this polyamic acid solution was heated at a temperature of about 70 ° C., and the viscosity was adjusted. The viscosity decreased to 7 poise in 5 hours, and a low viscosity polyamic acid solution (A) was obtained.

To 20 g of this polyamic acid solution (A), 0.2 g of 2,6-di (p-azidobenzal) 4-hydroxylcyclohexanone (0.
1.8 g (10.5 mmol) of 3- (N, N-dimethylamino) propyl methacrylate was added, and then 1 μm
A photosensitive polymer composition (nonvolatile content: 13.6% by weight) was obtained by pressurizing using a filter having holes.

Then, this composition was applied onto a silicon wafer with a spinner and dried at 80 ° C. for 30 minutes to obtain a photosensitive film having a thickness of 5 μm. This film is contact exposed using a 20μm line-and-space striped photomask and 500W from a distance of 30cm.
It was irradiated with the high pressure mercury lamp for 10 seconds. After exposure N-methyl-2-
It was developed with a mixed solution of 4 volumes of pyrrolidone and 1 volume of ethanol, and then rinsed with ethanol to obtain a relief pattern.

Then, heat treatment was performed at 180 ° C. for 30 minutes and at 400 ° C. for 60 minutes in a nitrogen atmosphere to obtain a polyimide relief pattern having a film thickness of 2.5 μm. At this time, the pattern firmly adhered to the substrate, and the photomask pattern was faithfully transferred.

Example 2 To 20 g of the polyamic acid solution (A) used in Example 1, 2,6-
Di (p-azidobenzal) 4-carboxylcyclohexanone 0.21 g (0.5 mmol), 3- (N, N-dimethylamino) propyl methacrylate 1.8 g (10.5 mmol) were added, and then pressure was applied using a filter with 1 μm pores. Thus, a photosensitive polymer composition (nonvolatile content: 13.6% by weight) was obtained.

Then, patterning was performed by the same operation as in Example 1, and a clear pattern could be obtained.

Example 3 In the same manner as in Example 1, 10 g (0.05 mol) of 4,4'-diaminodiphenyl ether was added to N-methyl-2-pyrrolidone 66.
Dissolve in 5 g, then meta-terphenyl-3,4,3 ", 4"-
18.5 g (0.05 mol) of tetracarboxylic dianhydride was added to synthesize a polyamic acid solution. The obtained polyamic acid solution had a nonvolatile content of 30% by weight and a viscosity of 1,500 poise (25 ° C).
It was. Next, this polyamic acid solution was heated at a temperature of about 70 ° C., and the viscosity was adjusted to decrease to 15 poise in 8 hours, and a high-concentration and low-viscosity solution (B) was obtained.

To 20 g of this polyamic acid solution (B), 0.34 g of 2,6-di (p-azidobenzal) 4-carboxylcyclohexanone
(0.85 mmol), 3- (N, N-dimethylamino) propylmethacrylate 3.6 g (21 mmol) was added, and then 1
A photosensitive polymer composition (nonvolatile content: 25.1% by weight) was obtained by pressurizing using a filter having a pore size of μm.

Then, patterning was performed by the same operation as in Example 1, and a clear pattern could be obtained.

Example 4 To 20 g of the polyamic acid solution (B) obtained in Example 3, 2,6
-Di (p-azidobenzal) 4-methylolcyclohexanone 0.16 g (0.4 mmol) 2- (N, N-dimethylamino) ethyl methacrylate 3.3 g (21 mmol) was added,
Then, a photosensitive polymer composition (nonvolatile content: 26.0% by weight) was obtained by pressurizing using a filter having 1 μm holes.

Then, patterning was performed by the same operation as in Example 1, and a clear pattern could be obtained.

Comparative Example 1 4,4'-diaminodiphenyl ether 10 g (0.05 mol),
Using 10.9 g (0.05 mol) of pyromellitic dianhydride and 49 g of N-methyl-2-pyrrolidone, a polyamic acid solution having a nonvolatile content of 30% by weight and a viscosity of 2,000 boaz (25 ° C.) was obtained in the same manner as in Example 1. It was When the viscosity of this polyamic acid solution was adjusted by heating at a temperature of about 80 ° C., a polyamic acid solution (E) having a poise reduced to 50 poise in 30 hours was obtained.

Next, to 20 g of this polyamic acid solution (E), 2,6-di (p
-Azidobenzal) 4-hydroxylcyclohexanone
0.27 g (0.7 mmol), 2.5 g (14,6 mmol) of 3- (N, N-dimethylamino) propylmethacrylate were added to 1 μm.
A photosensitive polymer composition (nonvolatile content: 26% by weight) was obtained by pressurizing using a m-hole filter. Next, patterning was performed by the same operation as in Example 1, and a clear pattern could be obtained.

Comparative Example 2 4,4'-diaminodiphenyl ether 10 g (0.05 mol),
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 14.
7 g (0.05 mol) and 70 g of N-methyl-2-pyrrolidone were synthesized in the same manner as in Example 1 to obtain a nonvolatile content of 30% by weight,
A polyamic acid solution having a viscosity of 5,000 Boaz (25 ° C.) was obtained.
Next, when this polyamic acid solution was heated at a temperature of around 80 ° C and the viscosity was adjusted, the decrease in viscosity stopped at around 200 poise and became constant, and when heating was continued, the solution began to become turbid and the viscosity On the contrary, it increased and it was not possible to obtain a low viscosity solution.

Comparative Example 3 4,4'-diaminodiphenyl ether 10 g (0.05 mol),
3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 16.1 g (0.05 mol), N-methyl-2-pyrrolidone 60.9 g
Was synthesized in the same manner as in Example 1 to obtain a polyamic acid solution having a nonvolatile content of 30% by weight and a viscosity of 2,000 poise (25 ° C.). When this polyamic acid solution was heated at a temperature of about 80 ° C. to adjust the viscosity, a polyamic acid solution (F) reduced to 60 poise (25 ° C.) in 20 hours was obtained.

Next, to 20 g of this polyamic acid solution (F), 2,6-di (p
-Azidobenzal) 4-carboxyl cyclohexanone
Add 0.46 g (1.15 mmol), 3- (N, N-dimethylamino) propyl methacrylate 3.9 g (22.8 g mmol) and add
A photosensitive polymer composition (nonvolatile content: 25% by weight) was obtained by applying pressure using a filter having a pore size of μm. Next, patterning was performed by the same operation as in Example 1, and a clear pattern could be obtained.

Next, the photosensitive polymer compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were coated on a glass substrate, dried, and then heat-treated at 400 ° C. for 1 hour to prepare a film. The film characteristics after peeling and curing were evaluated by the test methods shown below.

Test method (1) Weight reduction start temperature Using the above film (10 mg), raise the temperature in air by a differential thermal balance at 10 ° C.
It was measured at / min.

(2) Weight reduction rate Using 80 mg of the above film, the same equipment as in (1) was used.
The weight loss rate after holding at 0 ° C / 30 minutes was measured.

(3) Modulus of elasticity The film was used as a strip-shaped test piece of 5 mm × 5 mm, and the modulus of elasticity was measured using a viscoelasticity measuring device.

The change in viscosity (measured at 25 ° C) of the photosensitive polymer composition was also tracked.

The above results are shown in Table 1.

(Effects of the Invention) The photosensitive polymer composition according to the present invention can have a high concentration and a low viscosity in a solution state, and also has good storage stability, heat resistance and flexibility of a final cured product. It has excellent film properties such as properties.

[Brief description of drawings]

FIG. 1 shows the intermediate product 3,4,3 ″, 4 ″ − manufactured in the reference example.
¹ H-NMR spectrum of tetramethyl-m-terphenyl, FIG. 2 is the ¹⁸ C-NMR spectrum of its 3,4,3 ″, 4 ″ -tetramethyl-m-terphenyl, and FIG. 3 is a reference example. Infrared absorption spectrum of m-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic acid, FIG. 4 shows m-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic acid tetramethyl prepared in Reference Example. ¹ H-NMR spectrum of ester, FIG. 5 shows infrared of m-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic acid-3,4,3 ″, 4 ″ -dianhydride prepared in Reference Example The absorption spectrum and FIG. 6 are m-terphenyl-3,4,3 ″, 4 ″ -tetracarboxylic acid-3,4,3 ″, 4 ″-prepared in Reference Example.
¹ shows a ¹ H-NMR spectrum of dianhydride.

Front Page Continuation (72) Inventor Shunichiro Uchimura 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Sato Court 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Factory (72) Inventor Daisuke Makino 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (1)

[Claims] 1. A photosensitive polymer composition containing a polyamic acid, a bisazide compound and an amine compound having a carbon-carbon double bond, wherein meta-terphenyl-3,4,3 ″, 4 is added to the acid component as polyamic acid. A photosensitive polymer composition comprising a polyamic acid obtained by using "-tetracarboxylic dianhydride.