JP3369344B2 - Photosensitive resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition useful as a protective insulating film for semiconductor devices, an alignment film for liquid crystal devices, an insulating film for multilayer printed circuit boards and the like.

[0002]

2. Description of the Related Art Conventionally, a polyimide-based material is known as a heat-resistant photosensitive material. For example, an ester bond (for example, JP-A-49-
Negative type in which a group capable of photocrosslinking is introduced by means of 115541, JP-A-55-45746) or an ionic bond (JP-A-54-145794) is well known. On the other hand, for positive photosensitive polyimide: Introducing o-nitrobenzyl ester into the side chain (J. Appl. Polym. Sci., 33 , 1763
(1987)), and a photoacid generator added as a photosensitizer to a polyamic acid silyl ester.

By the way, the positive-type photosensitive polyimide which can be developed with an alkaline aqueous solution can be used in the existing photoresist developing apparatus, and is characterized in that the film does not swell during development.

[0004]

However, since the positive type photosensitive polyimide has increased solubility in an alkaline aqueous solution by light irradiation, the exposed portion is dissolved to form a pattern when developed with an alkaline aqueous solution. The conventional positive-type photosensitive polyimide has problems that the resin in the unexposed area is also dissolved in the alkaline aqueous solution to some extent to cause film reduction, the film thickness after development varies, and the dimensional accuracy is not good. In addition, since the magnitude of the change in solubility due to exposure varies depending on the type of polyimide used as a raw material, the sensitivity may be poor and the resolution may be lowered depending on the raw material.

Therefore, an object of the present invention is to provide a positive photosensitive resin composition which can be developed with an alkaline aqueous solution, has little film loss due to development, has good sensitivity, and can form a heat resistant polyimide film. To do.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that when a diazonaphthoquinone sulfonic acid ester and a phenol novolac resin are blended with a polyamic acid silyl ester, it is exposed to light. The change in solubility in an alkaline aqueous solution can be increased, and a photosensitive resin composition having good sensitivity can be obtained, and this resin composition has excellent properties such as little film loss even after development after exposure. Find out
The present invention has been completed.

The present invention provides (A) the following general formula (1):

[Chemical 6]

[In the formula, plural Rs may be the same or different, and the following general formula (2):

[Chemical 7]

(In the formula, plural R ^{1 s} may be the same or different and each is —H or a monovalent organic group having 1 to 8 carbon atoms.), And X is 4 Is a divalent organic group, Y is a divalent organic group, and m is an integer of 5 to 80, preferably 25 to 60. ] The polyimide resin precursor represented by,

(B) The following general formula (3):

[Chemical 8]

(Wherein R ² is an organic group having 1 to 50 carbon atoms, and i is an integer of 1 to 7), a photosensitive diazoquinone compound represented by the following general formula (4):

[0012]

[Chemical 9]

(Wherein R ² is as described above and j is an integer of 1 to 7), or a photosensitive diazoquinone compound represented by the formula, or a combination thereof, and

(C) The following general formula (5):

[Chemical 10]

(In the formula, R ³ is --H or 1 to 6 carbon atoms.
Is an organic group, and n is an integer of 2 to 100. The present invention provides a photosensitive resin composition containing a phenol novolac resin represented by the formula (1).

In the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate, dried, and the formed coating film is exposed to light.
Provided is a method for forming a patterned polyimide film, which comprises developing with alkali and curing the resulting patterned polyimide film.

(A) Polyimide Resin Precursor The polyimide resin precursor which is the component (A) of the present invention is represented by the above general formula (1). When a plurality of X's contained in one molecule of the polyimide resin precursor are present, they may be the same or different, and when a plurality of Y's are present, they may be the same or different.

X in the above general formula (1) is a tetravalent organic group, and a typical example thereof is:

[0019]

[Chemical 11] However, the present invention is not limited to these.

Y in the general formula (1) is a divalent organic group, for example, the following general formula (6):

[Chemical 12]

(In the formula, R ⁴ is --H, --Cl, --CONH ₂ ,
Alternatively, it is an alkyl group having 1 to 3 carbon atoms such as —CH ₃ , —C ₂ H ₅ , or —C ₃ H ₇ . ) Group represented by
The following general formula (7):

[0022]

[Chemical 13]

(In the formula, R ⁵ is a single bond, —O—,
--SO _2- , --S--, or, for example, --CH _2- , --C (C
_{H 3) 2 -, - C} (CF 3) 2 - is a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, such as. Further, a plurality of R ⁴ may be the same or different and are as described above. ), The following general formula (8):

[0024]

[Chemical 14]

(In the formula, a plurality of R ⁴ may be the same or different as described above, and a plurality of R ⁵ may be the same or different as described above.) Formula (9):

[0026]

[Chemical 15]

(In the formula, a plurality of R ⁴ may be the same or different and is as described above, and R ⁵ is as described above.), The following general formula (10):

[0028]

[Chemical 16]

(In the formula, a plurality of R ⁶ may be the same or different, and examples thereof include an alkylene group having 3 to 4 carbon atoms such as —C ₃ H ₆ —, —C ₄ H ₈ —, a phenylene group, or formula:

[0030]

[Chemical 17] Is a group represented by. A plurality of R ^{7 s} may be the same or different and are, for example, an alkyl group having 1 to 3 carbon atoms such as —CH ₃ , —C ₂ H ₅ , or —C ₃ H ₇ or a phenyl group. k
Is an integer from 1 to 40. Group having a siloxane bond represented by the following general formula (11):

[0031]

[Chemical 18]

(In the formula, a plurality of R ⁷ may be the same or different and are as described above, R ⁸ is an ethylene group or a phenylene group, and R ⁹ is, for example, —C ₃ H ₆ —, — C
₄ H ₈ - alkylene group having 3-4 carbon atoms, such as. And a group having a silethylene bond or a silphenylene bond represented by the formula (1).

R in the above general formula (1) is the above general formula (2)
And a plurality of R's may be the same or different. Further, a plurality of R ^{1 s} in the general formula (2) may be the same or different, and are —H or a monovalent organic group having 1 to 8 carbon atoms, specifically, a hydrogen atom; Alkyl groups such as groups, ethyl groups, propyl groups, butyl groups;
For example, alkenyl group such as vinyl group, allyl group, butenyl group; aryl group such as phenyl group, tolyl group;
Part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, an alkoxy group, etc., for example, a chloromethyl group, a chloropropyl group, 3,3,
Examples thereof include 3-trifluoropropyl group, 2-cyanoethyl group, methoxy group, and ethoxyethyl group, but are not limited thereto.

The polyimide resin precursor represented by the above general formula (1) can be synthesized according to a known method (Japanese Patent Publication No. 43-18790). For example, the following general formula (12):

[0035]

[Chemical 19] (In the formula, X is as described above.) And a tetracarboxylic dianhydride represented by the following general formula (13):

[0036]

[Chemical 20]

(In the formula, plural Rs may be the same or different and are as described above, and Y is also as described above.) The silyldiamine compound represented by the formula is suitable so as to be almost equimolar. It is manufactured by mixing in a different inert solvent and usually reacting at 0 to 40 ° C. Usually the reaction time is
It takes about 1 to 24 hours. However, the manufacturing method is not limited to this.

Further, as the inert solvent used in the above-mentioned production method, a solvent which dissolves the produced polyimide resin precursor is desirable, and specifically, for example, N-methyl-2-pyrrolidone, N, N -Dimethylacetamide, dimethylformamide, hexamethylphosphoramide, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, Examples thereof include organic solvents such as cyclohexanone, γ-butyrolactone, butyl cellosolve acetate, toluene, xylene, anisole, methylanisole and ethylphenyl ether. Moreover, these are 1 type individually or 2
Combinations of more than one species can be used.

Examples of the tetracarboxylic dianhydride represented by the general formula (12) include, for example, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis
[4- (3,4-Dicarboxyphenoxy) phenyl] propanoic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) perfluoropropanoic acid dianhydride, bis (3,4-dicarboxy Phenyl) dimethyl silane dianhydride, 1,3-bis (3,4
-Dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, etc., which may be used alone or
Combinations of more than one species can be used.

The silyldiamine compound represented by the general formula (13) is, for example, the following general formula (14):

[Chemical 21] (In the formula, Y is as described above.) And the following general formula (15):

[0041]

[Chemical formula 22] (In the formula, a plurality of R ¹ may be the same or different and is as described above.)
It can be produced by condensing with a base.

Examples of the diamine compound represented by the above general formula (14) include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl ether, 2,2- bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4 -Bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthio )
Benzene, 1,4-bis (m-aminophenylthio ) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-amino) Phenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- Bis [3-methyl-4
-(4-Aminophenoxy) phenyl] ethane, 1,1-bis [3
-Chloro-4- (4-aminophenoxy) phenyl] ethane,
1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-amino) (Phenoxy)
Phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-amino) Aromatic diamine compounds such as phenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane; for example, the following formula:

[0043]

[Chemical formula 23] A diamine compound having a siloxane bond represented by:
For example, the following formula:

[0044]

[Chemical formula 24] Examples thereof include diamine compounds having a silethylene bond or a silphenylene bond represented by, but are not limited to these. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

In the composition of the present invention, the polyimide resin precursor (A) may be used alone or in combination of two or more.

(B) Photosensitive diazoquinone compound The photosensitive diazoquinone compound which is the component (B) of the present invention is
It is represented by the above general formula (3) or (4).

R ² in the general formula (3) or (4) is a monovalent to monovalent organic group having 1 to 50 carbon atoms, and among them, a group having a benzene ring is preferable. As the photosensitive cyanazoquinone compound, specifically,

[0048]

[Chemical 25]

(Where Z is the formula:

[Chemical formula 26] Indicates. ) Etc. are illustrated.

The amount of the photosensitive diazoquinone compound (B) compounded is preferably 2 to 100 parts by weight of the component (A).
It is 100 parts by weight, more preferably 4 to 60 parts by weight.

In the composition of the present invention, the photosensitive diazoquinone compound (B) may be used either individually or in combination of two or more.

(C) Phenol Novolac Resin The phenol novolac resin which is the component (C) of the present invention is
It is represented by the above general formula (5). Further, plural R ³ in the phenol novolac resin may be the same or different.

R ³ in the above general formula (5) is a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. Specific examples of R ³ include —CH ₃ , —CF ₃ , and —C ₂ H.
₅ include -C ₃ H _7, or the like.

The phenol novolac resin represented by the above general formula (5) can be obtained, for example, by the following general formula (1
6):

[Chemical 27]

The compound can be produced by a hydroformylation reaction of a phenol derivative represented by the formula (wherein R ³ is as described above) and an aqueous formaldehyde solution or anhydrous formaldehyde, but is not limited to this production method. Not a thing.

Examples of the catalyst used in the above-mentioned production method include organic acids such as oxalic acid and p-toluenesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. These catalysts are used alone or in combination of two or more.

The amount of the phenol novolac resin (C) to be blended is preferably 1 to 100 parts by weight of the component (A).
It is 100 parts by weight, more preferably 3 to 50 parts by weight.

In the composition of the present invention, the phenol novolac resin (C) can be used alone or in combination of two or more.

Photosensitive Resin Composition The photosensitive resin composition of the present invention is prepared by dissolving the above-mentioned polyimide resin precursor (A), photosensitive diazoquinone compound (B) and phenol novolac resin (C) in a suitable organic solvent. The solution is stored and used.

As the above-mentioned organic solvent, the organic solvent used in the production of the polyimide resin precursor (A) as exemplified above is preferably used.
Used alone or in combination of two or more. Also,
The amount of the organic solvent used is usually 100 to 2000 parts by weight per 100 parts by weight of the polyimide resin precursor (A).

A solution obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent is formed on a substrate such as a silicon wafer, a metal plate, a glass plate or a ceramic substrate by a known method such as spin coating, dipping or printing. After forming a coating film by drying, a polyimide-based protective film having excellent heat resistance and the like is formed through various steps of exposure, alkali development and curing.

The coating film is formed by drying by, for example, a drier,
It can be carried out by prebaking at a temperature of 30 to 180 ° C. for several minutes to several hours using a heating means such as a hot plate to remove most of the organic solvent in the coating film.

The exposure is carried out by placing a mask on the film formed above and irradiating it with light such as visible light or ultraviolet light for several seconds to several minutes.

After the exposure, a relief pattern can be obtained by dissolving and removing the exposed portion with a developing solution. Here, an alkaline aqueous solution is preferably used as the developer, and examples of the alkaline aqueous solution used include an aqueous solution of tetramethylammonium hydroxide.

Further, the resin of the relief pattern formed by development is heated by a heating means such as a dryer or an electric furnace at a temperature of usually 200 to 500 ° C., preferably 300 to 400 ° C. for several tens of minutes to several hours. By doing so, a patterned polyimide film can be formed.

[0066]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Preparation of Polyimide Resin Precursor Solution Under a nitrogen atmosphere, 2,2-bis (3,4-dicarboxyphenyl)
To 22.2 g (0.050 mol) of perfluoropropanoic anhydride,
Diethylene glycol dimethyl ether 39.5g and N, N-
Dimethylacetamide 39.5 g was added. The resulting mixture was further mixed with N, N'- bis (trimethylsilyl) -4,4'-diaminodiphenyl ether 15.51 g (0.045 mol) and 1,3-
Bis [3- (N-trimethylsilyl) aminopropyl] -1,
1,3,3-Tetramethyldidyloxane 1.98 g (0.005 mol)
20 g of diethylene glycol dimethyl ether and N, N-
A solution dissolved in 20 g of dimethylacetamide was added dropwise while cooling so that the reaction temperature did not exceed 40 ° C. After completion of dropping, the mixture was further stirred for 12 hours. Thus the formula:

[0068]

[Chemical 28]

(Where Y is the following formula (17):

[Chemical 29] A group represented by or the following formula (18):

[Chemical 30] The molar ratio of the group represented by the formula (17) to the group represented by the formula (18) is 9: 1. Further, m is 34 on average. )

A solution of a polyimide precursor (number average molecular weight: 1.21 × 10 ⁴ , weight average molecular weight: 2.68 × 10 ⁴ ) represented by
(Viscosity at 25 ℃: 4500 cP) was obtained (nonvolatile matter 25
%).

[0071] and producing o- cresol 0.5 mol of the photosensitive diazoquinone compound, 1-na Futokinon 2-diazide
-5-Sulfonyl chloride (0.51 mol) was reacted with 1,2-dioxane in the presence of triethylamine, washed with water and dried to obtain the compound represented by the formula:

[0072]

[Chemical 31] A photosensitive diazoquinone compound represented by

Preparation of cresol novolac resin m-cresol / p-cresol ratio = 45/55, cresol /
M-Cresol, p-cresol and formalin were reacted with oxalic acid as a solvent at a molar ratio such that the formalin ratio = 1 / 0.75. After completion of the reaction, the reaction mixture obtained is neutralized, washed with water and dehydrated to obtain the formula:

[0074]

[Chemical 32] (In the formula, n is 24 on average.) A cresol novolac resin (number average molecular weight: 1.02 × 10 ³ , weight average molecular weight: 2.91 × 10 ³ ) was obtained.

Example 1 A photosensitive resin composition was prepared by mixing 48.0 g of the polyimide resin precursor solution obtained above, a photosensitive diazoquinone compound 3.0, and 3.0 g of cresol novolac resin. The composition was coated on a silicon wafer with a spin coater and soft-baked with a hot plate to obtain a photosensitive resin film. This is exposed with a high pressure mercury lamp (exposure amount 600m
J / cm ² ), followed by development with a 2.3% aqueous solution of tetramethylammonium hydroxide and rinsing with pure water, and then the film thicknesses of the fog light portion and the non-fog light portion and their respective dissolution rates were determined.
The results are shown in Table 1.

Comparative Example 1 A photosensitive resin composition was prepared by mixing 48.0 g of the polyimide resin precursor solution obtained above with a photosensitive diazoquinone compound 3.0. The composition was coated on a silicon wafer with a spin coater and soft-baked with a hot plate to obtain a photosensitive resin film. This was exposed with a high-pressure mercury lamp (exposure amount 600 mJ / cm ² ), followed by development with a 2.3% aqueous solution of tetramethylammonium hydroxide and rinsing with pure water. The dissolution rate of each was determined. The results are shown in Table 1.

[0077]

[Table 1]

In Comparative Example 1 described above, the dissolution rate of the unexposed area is high and the film loss is large, but in Example 1, the film loss is small, so that the composition of the present invention is superior. .

[0079]

EFFECT OF THE INVENTION The photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution, gives a heat-resistant film with good sensitivity and less film loss. Therefore, the composition of the present invention is useful for forming a protective film for electronic parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/023 511 G03F 7/023 511 7/075 511 7/075 511 7/40 501 7/40 501 H01L 21/027 H01L 21 / 312 B 21/312 H05K 3/28 D 23/29 H01L 21/30 502P 23/31 23/30 C H05K 3/28 (56) Reference JP 5-204156 (JP, A) JP JP 4 -284455 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (2)

(57) [Claims] 1. (A) The following general formula (1): [In the formula, plural Rs may be the same or different, and the following general formula (2): (In the formula, plural R ^{1 s} may be the same or different and are —H or a monovalent organic group having 1 to 8 carbon atoms.), And X is a tetravalent organic group. Is a group, Y is a divalent organic group, and m is an integer of 5 to 80. ] (B) The following general formula (3): (In the formula, R ² is an organic group having 1 to 50 carbon atoms, and i is an integer of 1 to 7.) A photosensitive diazoquinone compound represented by the following general formula (4): (Wherein R ² is as described above and j is an integer of 1 to 7), or a photosensitive diazoquinone compound represented by the following, or (C) the following general formula (5): Chemical 5] (In the formula, R ³ is —H or an organic group having 1 to 6 carbon atoms, and n is an integer of 2 to 100.) A photosensitive resin composition containing a phenol novolac resin . 2. A composition according to claim 1 is applied onto a substrate, dried, the formed coating film is exposed to light, and alkali-developed, and the resulting patterned polyimide film is cured. A method for forming a patterned polyimide film.