JPH0470661A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain stabler quality, higher sensitivity and better film characteristics by using a specific polyamide acid compd. having actinic functional groups at both terminals, an amide compd. contg. carbon-carbon double bonds which are soln. at ordinary temp. and can be polymerized by actinic radiations and a sensitizer having a specific absorption max. wavelength as essential components. CONSTITUTION:This compsn. contains the polyamide acid compd. which is expressed by formula I and has the actinic functional groups P* at both terminals, the amide compd. contg. carbon-carbon double bonds which are soln. at ordinary temp. and can be polymerized by the actinic radiations and the sensitizer having 330 to 500nm absorption max. wavelength (lambda max) as the essential components. In the formula I, (m)=10 to 1000 integer; R3, R4 denote the arom. cyclic group. The actinic functional groups P* are expressed by formula II where (n) denotes 2 to 5; R1 denotes H, CH3, R2 denotes a residual org. group. The stabler quality, the higher sensitivity and the better film characteristics are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly sensitive photosensitive boimide resin composition and a method for producing the same.

[Conventional technology] Conventionally, surface protection films of semiconductor elements, glabella insulating films, etc.
Polyimide resin is used because it has excellent heat resistance and outstanding electrical and mechanical properties. However, in recent years, semiconductor devices have become more highly integrated and larger, sealing resin packages have become thinner and smaller, and solder With the shift to surface mounting methods using Waflow, there is a demand for significant improvements in heat cycle resistance, heat shock resistance, etc., and polyimide resins with even higher performance are now required.

On the other hand, technology that imparts photosensitivity to polyimide resin itself has recently attracted attention.

Using polyimide resins that have been given these photosensitizers not only simplifies the pattern creation process compared to polyimide resins that have not been given photosensitivity, but also eliminates the need for highly toxic etching solutions, making them safer. It is also excellent in terms of pollution, and photosensitization of polyimide resin is expected to become an important technology.

As the photosensitive polyimide resin, for example, a polyimide precursor composition to which a photosensitive group is added with an ester group having a structure as shown in the following formula (A) (for example, Japanese Patent Publication No. 55-41422
(No. 2003) or a polyamic acid having a structure as shown in the following formula (B) by adding a compound containing a carbon-carbon double bond and an amino group that can be dimerized or polymerized by actinic radiation, or a quaternized salt thereof. compositions (for example, Japanese Patent Publication No. 1983-
52822), etc. are known.

All of these are dissolved in a suitable organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and then heat-treated to form a polyimide. It is a coating.

However, such conventional compositions have the following drawbacks. That is, the composition shown in (A) is produced through an extremely complicated process of first causing an esterification reaction between a tetracarboxylic dianhydride and an alcohol having a photosensitive group, and then performing an amidation reaction with a diamine. ,
It was difficult to stabilize the product. However, since ester bonds have a strong bonding force, they have the advantage that spray development (a method of rapid development in a short period of time by vigorously spraying a developer) is possible. However, because the bond strength is too strong, 400
Even at high temperatures of .degree. C. or higher, the photosensitive groups could not be completely removed, leading to blackening of the polyimide film and deterioration of the film's physical properties (strength, elongation, etc.). On the other hand, in the composition shown in (B), the manufacturing process is extremely simple because it is only necessary to add and mix the photosensitizer with the polyamic acid, but the ionic bonding force between the polyamic acid and the photosensitizer is extremely weak. The disadvantage is that puddle development (a method of developing by dropping a developing solution onto a stationary film to be developed) is required, which takes some time. Furthermore, the varnish exhibits a large viscosity change at room temperature and lacks storage stability, making it unsatisfactory for application to semiconductor manufacturing processes. On the other hand, since the bonding force is weak, the photosensitive group is easily removed by heating, which has the advantage that the polyimide film has excellent film properties. However, (A), (B
) has an exposure sensitivity of 200 to 400 mJ/c.
m2 (i-line contact exposure machine, full spectrum, thickness 1
0 μm), which has become insufficient to meet the demands for higher sensitivity accompanying recent technological advances.

[Problems to be Solved by the Invention] An object of the present invention is to provide a photosensitive resin composition that has uniform quality, extremely high sensitivity, and excellent film properties, by an extremely simple method. .

[Means for Solving the Problems] The present invention provides (A) a polyamic acid compound (I) having actinic radiation functional groups P'' at both ends, (wherein n = 2,3 Rx: )l, CH3R2
: organic residue) (where m = an integer of 10 to 10,000, R
3, R4: aromatic cyclic group) (B) an amide compound containing a carbon-carbon double bond that can be polymerized by actinic radiation, (C) a sensitizer with a maximum absorption wavelength (^max) of 330 to 500 nm. This is a photosensitive resin composition characterized in that it is a component.

[Function] The aromatic tetracarboxylic acid or its derivative used in the present invention is represented by the following formula (It) (R3: aromatic cyclic group), for example, pyromellitic dianhydride, benzene-1,2° 3.4-tetracarboxylic dianhydride, 3.3', 4.
4'-benzophenonetetracarboxylic dianhydride, 2.
2',3.3-benzophenonetetracarboxylic dianhydride, 2°3.3',4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, Naphthalene-1,2,5,6-tetracarboxylic dianhydride, Naphthalene-1,2,4,5
-Tetracarboxylic dianhydride, naphthalene-1,4,5
, 8-tetracarboxylic dianhydride, naphthalene-1,2
, 6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,buhexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4 ,8
-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-cyclonaphthalene-1.4,5.8 -Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1゜4.5.8-Tetracarboxylic dianhydride, 2,3,
6.7-tetrachloronaphthalene-1.4,5.8-tetracarboxylic dianhydride, 1,4,5.8-tetrachloronaphthalene-2,3°6.7-tetracarboxylic dianhydride, 3.3', 4.4'-diphenyltetracarboxylic dianhydride, 2.2', 3.3'-diphenyltetracarboxylic dianhydride, 2,3.3', 4'-diphenyltetracarboxylic acid Dianhydride, 3.3", 4°4"-
ρ-terphenyltetracarboxylic dianhydride, 2.2″
, 3.3"-p-terphenyltetracarboxylic dianhydride, 2,3.3", 4"-P-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxylic dianhydride) phenyl)-propanihydride, 2,2-bis(3,
4-dicarboxyphenyl)-propanihydride, bis(2,3-dicarboxyphenyl)ether dianhydride,
Bis(3,4-dicarboxyphenyl) ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxy phenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxy phenyl)ethane dianhydride, perylene-2,
3,8,9-tetracarboxylic dianhydride, perylene-3
, 4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene- 1,2,7゜8-tetracarboxylic dianhydride, phenanthrene-1゜2.6.7-tetracarboxylic dianhydride, phenanthrene-1,2,9,1
0-tetracarboxylic dianhydride, cyclopencune-1,
2,3,4-tetracarboxylic dianhydride, pyrazine-2
, 3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, etc. However, it is not limited to these. Further, in use, one type or a mixture of two or more types may be used.

Examples of compounds having an actinic radiation-sensitive group P" used in the present invention include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, Methacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acrylate methacrylate, trimethylolpropane diacrylate, 1,3-diacryloylethyl-5-
Hydroxyethyl isocyanurate, 1,3-dimethacrylate-5-hydroxyethyl isocyanurate, ethylene glycol-modified pentaeryswatol monoacrylate, propylene glycol-modified pentaeryswatol triacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate Examples include, but are not limited to. When using these, one type or a mixture of two or more types may be used.

The aromatic diamine and/or its derivative used in the present invention is represented by the following formula (III), and (R4
: aromatic cyclic group, m = 0 to 2) diamine with m = 0, diaminocarboxylic acid with m = 1, m =
Diaminodicarboxylic acid (2) is used, and the amine component may be one type or a mixture of two or more types. Examples of the types of amines used include m-phenylene-
Diamine, 1-isopropyl 2,4-phenylene-diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diaminodiphenylethane, 3
, 3'-diamino-diphenyl ethane, 4,4'-diamino-diphenylmethane, 3.3'-diamino-diphenylmethane, 4.4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4.
4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl,
3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4.4"-diamino-p-terphenyl, 3.3"-diamino-p-terphenyl, bis (p-amino-cyclohexyl)methane, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-6-aminobentyl)benzene, p-bis(2-methyl-4- amino-pentyl)benzene, p-bis(1,1-dimethyl-5-amino-pentyl)benzene, 1,5-diamino-naphthalene, 2,6-cyamitunaphthalene, 2,4-bis(β-
amino-butyl)toluene, 2,4-diamino-toluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, I-xylylene-diamine, p
-xylylene-diamine, 2,6-cyamitopyridine, 2,5-diamino-pyridine, 2,5-diamino-1
, 3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2-dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine , hexamethylene-diamine, 2,5-dimethyl-hexamethylene-diamine, 3
-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 4,
4-dimethyl-hebutamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, ■, 10
-diamino-1,10-dimethyl-decane, 2,11-
Diamino-dodecane, 1,12-diamino-octadecane, 2,12-diamino-oftatecane, 2,17-diaminosiloxane, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino-4, Examples include, but are not limited to, 4'-dicarboxylic benzidine.

Examples of the amide compound containing a carbon-carbon double bond polymerizable by actinic radiation used in the present invention include N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-ethylmethacrylamide,
N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dibutylacrylamide, N-acryloylpipeTnodine, N-acryloylmorpholine,
Examples include, but are not limited to, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dimethylaminoethylmethacrylamide, N,N-dimethylaminepropylmethacrylamide, and N-vinylpyrrolidone. It's not something you can do. Further, in use, one type or a mixture of two or more types may be used.

The polyamic acid (I) of the present invention is synthesized using an amide compound containing a carbon-carbon double bond that can be polymerized by actinic radiation as a reaction solvent. When you want to synthesize a polyamic acid of
It can be obtained by first reacting 2 moles of a compound having *' and then further reacting 1000 moles of diamine (m).

Since the polyamic acid (I) has polyfunctional actinic radiation-sensitive groups P'' at both ends, the crosslinking density in the exposed area increases, and the non-crosslinked sensitive group P'' with good solubility is present in the unexposed area. Because of this, it is possible to increase the difference in solubility between exposed and unexposed areas, making it possible to increase sensitivity.Also, because the terminals of polyamic acid are protected with actinic radiation-sensitive group P4, polyamic acid No depolymerization occurred, and therefore a resin with good viscosity stability was obtained.

Furthermore, the use of the amide compound as a reaction solvent has not been practiced in the past.

Conventional reaction solvents are organic polar solvents whose functional groups have a dipole moment that does not react with acid anhydrides and diamines.

In addition to being inert to the system and solvent to the product, the organic polar solvent had to be solvent to at least one, preferably both, of the reaction components.

Typical solvents of this type include N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylformamide.
-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone, Examples include methylformamide, N-acetyl-2-pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and these solvents may be used alone or in combination. Other solvents that can be used in combination include benzene, benzonitrile, dioxane, butyrolactone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, xylene,
Conventional reaction solvents, in which non-solvents such as toluene and cyclohexane were used in combination as dispersion media for raw materials, reaction regulators, film smoothing agents, etc., were not sensitive to light. Therefore, when manufacturing conventional photosensitive resins,
In particular, a photosensitive component to light was added. However, since it is diluted with a large amount of reaction solvent, there is a limit to the improvement of the photosensitive group concentration.

According to the method of the present invention using the amide compound as a solvent, since the solvent itself is 100% photosensitive, the concentration of photosensitive groups is painfully high, and therefore, the photosensitivity can also be significantly increased. In addition, since the method for producing photosensitive resin according to the present invention only involves adding and mixing each component,
It was extremely simple, and the variation in quality was significantly reduced.

The sensitizer used in the present invention is a compound having a maximum absorption wavelength (max) of 330 to 500 nm. λi+ax
If the wavelength is less than 330 nm, light is absorbed by the polyamic acid itself and no photoreaction is possible, which is not preferable. On the other hand, if it is 500 nm or more, it is not preferable because it will undergo a photoreaction with visible light, making it necessary to set up a work place in a shielded room, and the ease of handling will deteriorate.

The sensitizer of the present invention is, for example, (IO- C10- Examples include, but are not limited to.

Further, in use, one type or a mixture of two or more types may be used.

An adhesion aid, a leveling agent, and various other fillers may be added to the photosensitive resin composition of the present invention.

The method of using the photosensitive resin composition according to the present invention is to first apply the composition to a suitable support such as a silicon wafer, ceramic, or aluminum substrate. Application methods include rotational coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, the coating film is dried by bath baking at a low temperature of 60 to 80°C, and then actinic radiation is irradiated in a desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible light, etc. can be used, but those having a wavelength of 200 to 500 nm are preferable.

Next, a relief pattern is obtained by dissolving and removing the unirradiated areas with a developer. As a developer, N-methyl-2
-pyrrolidone, N,N-dimethylacetamide, N,N
- Use dimethylformamide, methanol, isopropyl alcohol, water, etc. alone or in combination. As the developing method, methods such as spray, paddle, immersion, and ultrasonic waves can be used.

Next, the 1-norf pattern formed by development is rinsed. As a rinsing liquid, methanol, ethanol,
Use isopropyl alcohol, butyl acetate, etc.

Next, heat treatment is performed to form imide rings and obtain a final pattern with high heat resistance.

The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as an insulating film between the eyebrows of a multilayer circuit, a cover coat for a flexible steel clad plate, a solder resist film, a liquid crystal alignment film, and the like.

The present invention will be specifically explained below using Examples.

(Example 1) 322 g (1, Omol) of 3.3',4.4'-benzophenonetetracarboxylic dianhydride, 11.4 g (0.05 mol) of glycerol dimethacrylate, and 2890 g of N,N-dimethylacrylamide. g, and reacted at 506C for 16 hours. Then 4,4'
-diaminodiphenyl ether 200g (1, Omo
1) was added and reacted at 20°C for 6 hours.

612 parts by weight of the obtained polyamic acid solution (solid content: 1
00 parts by weight), Michler's ketone (λmax 365n
m) 5 parts by weight were added and dissolved at room temperature. The resulting composition was applied onto a silicon wafer using a spinner and dried in a dryer at 80°C for 1 hour to obtain a film of about 10μI.

This film is coated with Kodak's Photographic Step Tablet No. 2.21 Step (in this gray scale, as the number of steps increases, the amount of transmitted light is 1/1 of that of the previous step).
f2, so the larger the residual stage after development, the better the sensitivity) were stacked, irradiated with ultraviolet rays of 10,100 O/cm2, and then developed with 60 parts by weight of N-methyl-2-pyrrolidone and 40 parts by weight of methanol. When developed using a solution and further rinsed with isopropyl alcohol, the pattern remained up to 12 steps, and the exposure sensitivity was 3011J/
It was found that C1112 has high sensitivity.

In addition, when a pattern was created in the same manner using a resolution measuring mask (Toppan Test Chart No. 01) manufactured by Toppan Printing, the pattern was resolved down to 4 μm, indicating high resolution.

Next, it is coated separately on an aluminum plate, exposed to light on the entire surface, developed and rinsed, and further heated to 150.250.350°C.
After curing each film by heating for 30 minutes, the aluminum plate was removed by etching to obtain a film.

Tensile strength of the obtained film (JIS K-6760)
The thermal decomposition onset temperature (TGA) was as high as 400°C (the higher the better).

Next, the room temperature (23°C) of the obtained polyamic acid solution
When the viscosity change was measured, it was found that there was no viscosity change up to 14 days, indicating excellent viscosity stability at room temperature.

(Comparative Example 1) 3,3-dimethyl-4-methoxybenzophenone was used instead of Michler's ketone used in Example 1, but since the λ@ax of this sensitizer was 296 nm, the photoinitiation reaction could be carried out efficiently. It was found that the pattern was not practical and the entire pattern was washed away during development.

(Comparative Example 2) Tetraphenylporphyrin zinc complex was used instead of Michler's ketone used in Example 1, but this sensitizer
Since the maximum wavelength was 650 nm, a photoreaction occurred during the work, and a pattern could not be obtained by development.

(Comparative Example 3) N-methyl-2-pyrrolidone was used in place of the N,N-dimethylacrylamide used in Example 1, and all other ingredients were mixed in the same manner, but there was no photosensitivity at all.

Therefore, 60 parts by weight of dimethylaminoethyl methacrylate was further added as a compound having a carbon-carbon double bond and an amine group that can be dimerized or polymerized by actinic radiation. It was processed and evaluated in the same manner as in Example 1, but the step tablet had only 5 steps and the exposure sensitivity was 300 mJ/am.
The sensitivity was low at 2. Furthermore, when the viscosity change at room temperature (23° C.) was measured, it was found that the viscosity had decreased by 20% after 3 days.

(Comparative Example 4) After dissolving 290 g of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride and 244 g of 2-hydroxyethyl methacrylate in γ-butyrolactone, 150 g of pyridine was added as a catalyst, and the mixture was heated at 20°C. The mixture was reacted for 24 hours to obtain an esterified product. Next, 370 g of dicyclohexylcarbodiimide was added as an amidation catalyst, followed by 200 g of 4,4'-diaminodiphenyl ether, and the mixture was reacted at 20°C for 8 hours. Next, this slurry was separated by filtration, and the filtrate was added dropwise to 350 liters of ethanol with vigorous stirring to precipitate a polymer.
It was left to stand for 2 hours. The precipitate was filtered off, dried and ground.

The molecular weight of the obtained polymer was 6,500, which was much smaller than expected. Therefore, a polymer was synthesized again using the same method, but the molecular weight remained at 11,000 in this case as well. It was found that this method not only requires a long and complicated process, but also has large variations.

Next, this polymer was dissolved in N-methyl-2-pyrrolidone, and the same sensitizer as in Example 1 was added to obtain a photosensitive resin composition, which was evaluated in the same manner. There are only steps, and the exposure sensitivity is 360triJ.
/ctn2, the sensitivity was low.

[Effects of the Invention] The photosensitive resin composition according to the present invention is obtained by reacting a polyamic acid having a polymerizable carbon-carbon double bond at its terminal in an amide compound solvent containing a polymerizable carbon-carbon double bond. The polyamic acid terminal is photosensitive, and the solvent itself is 10
0% photosensitivity, the concentration of photosensitive groups is extremely high, and therefore the exposure sensitivity is 1% compared to conventional photosensitive resin compositions.
It is now possible to improve the performance by more than 0 times.

Furthermore, since the polyamic acid terminals are protected, it is possible to stabilize the viscosity of the resin composition.

Procedural amendment August 31, 1990

Claims (1)

[Claims] (1) (A) Polyamic acid compound [I] having actinic radiation functional group P^* at both ends, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n = 2, 3R_1:H, CH_3R_2: organic Residues) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, m = integer from 10 to 10,000, R_3, R_4: aromatic cyclic group) (B) Carbon-carbon double bonds that can be polymerized by actinic radiation The amide compound containing (C) has a maximum absorption wavelength (λmax) of 3
A photosensitive resin composition comprising as an essential component a sensitizer having a wavelength of 30 to 500 nm.