JPH03186847A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the heat resistant photosensitive polyimide resin compsn. with which the production process is simple and which is free from the fluctuation in products and allows spary development by constituting the compsn. of a specific polymer, and a sensitizer and/or initiator. CONSTITUTION:This compsn. consists of the polymer essentially consisting of the constitutional unit expressed by formula I and the sensitizer and/or initia tor. In the formula I, R1, R2 denote an arom. cyclic group; R3 denote -H, -CH3, -C2H5; R4 denotes -H-, -CH3, -C2H5, -CH2OH, -C6H5; (n) denotes 1 to 2; (m) denotes 0 to 2. The method for photosensitization which can take advantage of the excellent characteristics intrinsic to the polyimide resin as they are is established in this way and this method is simple. The resulted photosensitive resin compsn. withstands the spray development as well.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly heat-resistant photosensitive polyimide resin composition.

[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 reflow, there is a demand for significant improvements in heat cycle resistance, heat shock resistance, etc., and conventional polyimide resins have
It has become difficult to respond.

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 front piece composition to which a photosensitive group is added with an ester group having a structure as shown in the following formula (A) (Japanese Patent Publication No. 55-41422) or the following formula (B) A composition prepared 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 to a polyamic acid having the structure shown in 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. In the composition shown in (B), the manufacturing process is extremely simple because it is only necessary to add and mix a photosensitizer to polyamic acid.
4- Because the ionic bonding force between the photosensitive agent and the photosensitive agent is extremely weak, spray development (a method of rapid development in a short period of time by spraying a developing solution), which is possible with the composition shown in (A), is impossible. Ta.

[Problems to be Solved by the Invention] An object of the present invention is to provide a heat-resistant photosensitive polyimide resin composition that has a simple manufacturing process, has no product variation, and is spray developable.

[Means to solve the problem] The present invention relates to the following general formula (I) (In the formula, R1+ R2: aromatic cyclic group.

R3: H, CH3, -C2H5 R<nee H, -CH3, C2H5゜CH20H, -Ce H5 n: 1-2I m: 0-2) A polymer whose main component is a structural unit represented by It is a photosensitive resin composition consisting of an agent and/or an initiator.

[Function] The polymer used in the present invention is synthesized, for example, by the following method.

That is, an acid represented by the following form CI) (when n = 1) (when n = 2), an amine represented by the following form (TI), and the following form (III) + (OH3C \ N -C0-C=CI2...
CIII)/R-R3 and N-methylolacrylamide represented by [I
] and (TI), and then add (III) and further react. The reaction between CI) and (IT) is usually completed in several hours at room temperature, and (
The reaction with III) is completed in half an hour to several hours at 50-100°C. The reaction will complete more quickly if a catalyst is used, but it will proceed satisfactorily even without a catalyst. In this way, the reaction can be completed extremely easily and consistently.

In general formula (I), as the acid having an aromatic cyclic group in R1, tricarboxylic acid anhydride with n=1, tetracarboxylic dianhydride with n=2, etc. are used, and there is only one type of acid anhydride component. However, a mixture of two or more types may be used. Examples of the acid anhydride used include trimellitic anhydride, 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'-benzophenone tetracarboxylic 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 anhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,
5,6,7-hexahydronaphthalene-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-cyclonaphthalene-1. ,4,5
, 8-tetracarboxylic dianhydride, 2,3,6.7-
Titrachloronaphthalene-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 dianhydride Acid dianhydride, 3.3", 4.4"-p
-terphenyltetracarboxylic dianhydride, 2.2",
3.3"-p-terphenyltetracarboxylic dianhydride, 2,3°3",4"-1)-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxylic 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, l,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-4,5,1,0,11-tetracarboxylic dianhydride, perylene-5,6,11,1,2
-Tetracarboxylic dianhydride, phenanthrene-1,2
, 7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2゜9.10-tetracarboxylic dianhydride, cyclopentane-1 , 2,3,4-tetracarboxylic dianhydride, pyrazine-2゜3.5.6-tetracarboxylic dianhydride, pyrrolidine-2゜3.4.5-tetracarboxylic dianhydride, thiophene- Examples include, but are not limited to, 2°3.4.5-tetracarboxylic dianhydride.

In Formula 1m (II), as the amine having an aromatic cyclic group for R2, diamine with m = 0, diaminocarboxylic acid with m = 1, diaminodicarboxylic acid with m = 2, etc. are used, and the number of amine components is one type. However, a mixture of two or more types may be used. 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'-diamino-diphenylethane, 3,3'
-diamino-diphenylethane, 4,4'-diamino-
diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4'-diamino-diphenyl sulfide, 3
．． 3'-diamino-diphenyl sulfide, 4,4'-
Diaminodiphenylsulfone, 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-amino-cyclohexyl)methane
-β-amino~t-butylphenyl)ether, bis(
p-β-methyl-δ-aminopentyl)benzene, p-
bis(2-methyl-4-amino-pentyl)benzene,
p-bis(1,l-dimethyl-5-amino-pentyl)
Benzene, 1,5-diamino-naphthalene, 2,6-cyamitunaphthalene, 2,4-bis(β-amino-4-butyl)toluene, 2,4-diamino-toluene, m-xylene-2,5-diamine , p-xylylene-2゜5-diamine, m-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, hepta methylene-diamine,
2,5-dimethyl-hebutamethylene-diamine, 3-methyl-hebutamethylene-diamine, 4,4-dimethyl-
Hebutamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methylene-diamine, -nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,1.0-diamino-1,10 -dimethyl-decane, 2,11-diamino-dodecane, l, 12-diamino-octadecane, 2,
12diamino-octadecane, 2,17-diaminosiloxane, diaminosiloxane, 2,6-diamino-4-
Carboxylic benzene, 3,3'-diamino-4,
Examples include, but are not limited to, 4'-dicarboxylic benzidine.

The N-methylol acrylamides represented by formula 8 [1n] include N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylol acrylamide, N,N-dimethylol methacrylamide, N-
-Methylol-N-methylacrylamide, N-methylol-N-methylmethacrylamide, N-methylol-
Examples include, but are not limited to, N-ethylacrylamide and N-methylol-N-ethylmethacrylamide.

Sensitizers used in the present invention include benzophenone, acetophenone, anthrone, p,p'-tetramethyldiaminobenzophenone (Michler's ketone), phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-acetyl-p- Nitroaniline, p-nitroaniline, 2-ethylanthraquinone, 2-tert-butylanthraquinone, N-acetyl-4-nitro-1-naphthylamine, picramide, 1,2-benzanthraquinone,
3-Methyl-1,3-diaza-1,9-benzanthrone, p.

p'-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, 1゜2
-naphthoquinone, 2,5-bis-(4'-diethylaminobenzal)-cyclopentane, 2,6-bis-(4'
-diethylaminobenzal)-cyclohexanone, 2.
6-bis-(4'-dimethylaminobenzal)-4-methyl-cyclohexanone, 2,6-bis=(4'-diethylaminobenzal)-4-methyl-cyclohexanone, 4,4'-bis-(dimethyl amino)-chalcone, 4
, 4'-bis-(diethylamino)-chalcone, p-dimethylaminobenzylideneindanone, 1,3-bis-
(4'-dimethylaminobenzal)-acetone, 1,3
Examples include, but are not limited to, -bis-(4'-diethylaminobenzal)-acetone, N-phenyl-jetanolamine, N-p-tolyl-diethylamine, stisol compounds, coumarin compounds, etc. Or it can be used in combination.

14- Initiators used in the present invention include 2,2-dimethoxy-2-phenyl-ace]phenone, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-
14-(methylthio)phenyl]-2-morpholino-
1-propane, 3.3', 4.4'-tetra-(t-
butylperoxycarbonyl)benzophenone, benzyl, benzoin-isopropyl ether, benzoin-
Isobutyl ether, 4,4'-dimethoxybenzyl,
1,4-dibenzoylbenzene, 4-benzoylbiphenyl, 2-benzoylnaphthalene, methyl-〇-benzoylbenzoate, 2,2'-bis(O-chlorophenyl)-4゜4', 5,5'-tetraphenyl- 1,2
'-biimidazole, IO-butyl-2-chloroacridone, ethyl-4-dimethylaminobenzoate, dibenzoylmethane, 2,4-diethylthioxanthone, 3
, 3-dimethyl-4-methoxypenzophenone, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-I-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-I-one, 1-phenyl- 1,2-butanedione-2
-(O-methoxycarbonyl)oxime, 1-phenyl-propanebutanedione-2-(O-benzoyl)oxime, ], 2-diphenyl-ethanedione-1-(O-
benzoyl)oxime, 1,3-diphenyl-propanetrione-2-(O-benzoyl)oxime, 1-phenyl-3-ethoxy-propanetrione-2-(O-bezoyl)oxime, g+)cine compounds, oxacylone compounds These include, but are not limited to,
Can be used alone or in combination.

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

The method for 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 or a ceramic substrate. Application methods include rotation application using a spinner, spray application using a spray coater,
This can be done by dipping, printing, roll coating, etc. next,
After pre-baking at a low temperature of 60-80°C and drying the coating,
Actinic radiation is applied to the 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
- Dimethylformamide, methanol, isopropyl alcohol, water, etc. are used alone or in combination. Spray, paddle, immersion, and ultrasonic development methods are available, but spray development is the most effective because it takes the shortest development time, can be incorporated in-line into the process, and provides the cleanest finished pattern. preferable.

In spray development, the developer is sprayed under considerable pressure, so unless the coating film has zero or extremely low solubility in the irradiated areas, it will dissolve together with the unirradiated areas, leaving no relief pattern. Put it away. While many conventional compositions cannot be spray developed, the compositions of the present invention can be developed and can be directly incorporated into in-line processes.

Next, the relief pattern formed by development is rinsed. As the rinsing liquid, methanol, ethanol, isopropyl alcohol, butyl acetate, etc. are used. 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 interlayer insulating film for multilayer circuits, a cover coat for flexible copper clad boards, a solder resist film, a liquid crystal alignment film, and the like.

The present invention will be specifically explained below using Examples.

Example 1 A mixture of 57 g of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride, 33 g of 4,4'-diaminodiphenyl ether as an amine, and 10 g of silicone diamine represented by the following formula was N-
The mixture was poured into methylpyrrolidone and reacted at 20°C for 6 hours.

60 g of N-methylolacrylamide was added to the obtained polyamic acid and reacted at 80°C for 1 hour. The molecular weight of the obtained polymer was 24,000, which was as expected.

Next, 4 g of 2-(p-dimethylaminostyryl)benzoxazole and 8 g of N-phenylglycine were added and mixed and dissolved at room temperature to obtain a photosensitive resin composition.

The obtained composition was applied onto an aluminum plate using a spinner and dried at 65°C for 1 hour using a dryer.

This film is coated with a Kodak Photographic Step Tablet No. 2.21 Step (in this gray scale, as the number of steps increases, the amount of transmitted light increases by 17 steps from the previous step).
f2, so the larger the residual stage after development, the better the sensitivity).

Next, this was set in a spray developing machine and developed using a developer containing 60% by weight of N-methylpyrrolidone and 40% by weight of xylene. When the pattern was further rinsed with isopropyl alcohol, the pattern remained up to 12 steps, and the pattern remained with high sensitivity. I found out something.

Development time was only 30 seconds.

Next, the coating was applied onto a silicon wafer in the same manner as described above, the entire surface was exposed, development and rinsing steps were performed, and further 15
Each was heated and cured at 0.250°C and 350°C for 30 minutes.

For an adhesion test, I cut 100 pieces into a 1 mm square and tried to peel them off with cellophane tape, but not a single piece came off, indicating high adhesion.

Separately, it was coated on an aluminum plate, exposed to light over the entire surface, developed, rinsed, and cured with heat, and then the aluminum plate was removed by etching to obtain a film.

Tensile strength of the obtained film (JIS K-6760)
was as large as 16Kg/n+m2 (bigger is better), and the thermal decomposition onset temperature was as high as 400°C (higher is better).
.

Volume resistivity of the obtained film (JrSC-6481)
was as large as 3XiO16Ω・mark (the larger the better), and the dielectric constant was as low as 3.2 (IMH2) (the lower the better)
.

Comparative Example 1 Diethylaminomethacrylate 6 (1 g) was added to the polyamic acid in Example 1 and mixed at room temperature. Next,
2-(p-dimethylaminostyryl) as in Example 1
4 g of benzoxazole and 8 g of N-phenylglycine were added to obtain a photosensitive resin composition. An attempt was made to apply this composition to a silicon wafer, expose it to light, and develop it, but spray development dissolved not only the unexposed areas but also the exposed areas, and no relief pattern could be obtained.

Comparative Example 2 After dissolving 57 g of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride and 48 g of 2-hydroxyethyl methacrylate in γ-butyrolactone, 30 g of 7Pi 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, after adding 73 g of dicyclohexylcarbodiimide as an amidation catalyst, 4
．． 33 g of 4'-diaminodiphenyl ether and Example 1
10 g of the silicone diamine described in 21- was added and reacted at 20°C for 8 hours. Next, this slurry was separated by filtration, and the filtrate was added dropwise to 70 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 and initiator as in Example 1 were added to obtain a photosensitive resin composition, which was then coated, exposed, and developed in the same manner. did.

In this case, spray development is possible, and the development time is 30 seconds.
The sensitivity was as high as 11 steps.

However, when an attempt was made to heat-treat and evaluate the film in the same manner as in Example 1, the tensile strength of the film was 3K.
g/mm2 or less, and reliability could not be evaluated.

[Effects of the Invention] 22- According to the present invention, a photosensitization method has been established that allows the original excellent properties of polyimide resin to be utilized as they are.

Furthermore, the method was simple, and the resulting photosensitive resin composition was resistant to spray development and had excellent processability in terms of use.

Claims (1)

[Claims] (1) Polyamic acid represented by the following formula [I], ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [I] (In the formula, R_1, R_2: aromatic cyclic group, R3: -H, -CH_3 , -C_2H_5 R_4: -H, -CH_3, -C_2H_5, -CH_
2OH, -C_6H_5 n: 1 to 2, m: 0 to 2) A photosensitive resin consisting of a polymer whose main component is a structural unit represented by