JPH1192660A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition enabling the imidation reaction at a temperature as low as <=250 deg.C after the formation of a pattern, giving a coating film exhibiting high adhesiveness to a substrate and useful as a protecting insulation film for semiconductor elements by using a resin having a specific structure and setting its average molecular weight within a specific range. SOLUTION: This composition contains (A) 100 pts.wt. of a polyimide resin having a structure expressed by the formula I [X is a group of formula II, etc.; Y is composed of 30-100 mol.% of a bivalent aromatic group containing methacryloxy group and expressed by the formula III (R is methacryloyl of formula IV, OH, etc.), and 70-0 mol.% of a bivalent aromatic group of formula V (B is a group of the formula VI, etc.); Z is a bivalent siloxane-containing group expressed by formula VII ((b) is 5-80); (m) and (n) are each an integer and m/(m+n) is 0.70-0.98] and (B) 0.01-20 pts.wt. of a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition useful for forming a protective insulating film for a semiconductor device, an alignment film for a liquid crystal display device, an insulating film for a multilayer printed board, and the like.

[0002]

2. Description of the Related Art Conventionally, as a heat-resistant photosensitive material family, for example,
A material family comprising a polyamic acid and a dichromate (Japanese Patent Publication No. 49-17374), a material comprising a carboxyl group of a polyamic acid having a photosensitive group introduced through an ester bond (Japanese Patent Application Laid-Open No. 49-115541, JP 5
5-45746), a material comprising a polyamic acid and an amine compound having a photosensitive group (JP-A-54-1457).
No. 94), and a material comprising a carboxyl group of a polyamic acid with a photosensitive group introduced through a silyl ester bond (Japanese Patent Application Laid-Open No. 62-275129). These materials use a polyimide resin precursor, and after applying a light onto a predetermined base material to form a pattern by irradiating light, the imidization reaction usually proceeds at a temperature exceeding 300 ° C. This is to obtain a heat-resistant polyimide resin film. They are not suitable for forming a polyimide film on a substrate that cannot withstand such high temperatures.

On the other hand, photosensitive polyimides having a polyimide resin which has already been imidized as a basic skeleton have also been proposed. For example, an example in which a photopolymerizable functional group is introduced into a polyimide skeleton as a negative type (JP-A-60-7292)
5, JP-A-61-59334) and an example in which diazonaphthoquinone is mixed with a polyimide having a phenolic hydroxyl group as a positive type (JP-A-3-209478).
These materials do not require high-temperature treatment after film formation, but all have insufficient adhesion between the film formed on the substrate and the substrate formed by patterning, and these materials are especially used as electronic materials. If applied, it can cause serious problems such as metal corrosion.

[0004]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving the above-mentioned problems, and has been made after the formation of a pattern.
A highly reliable photosensitive resin composition that can be imidized at a low temperature of 250 ° C. or less and that the resulting film exhibits good adhesion to a substrate and is free from metal corrosion.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, the following composition has good sensitivity to light irradiation and easily forms a pattern. Can be performed, and an imidized film can be formed on a substrate by heat treatment at a relatively low temperature of 250 ° C. or less. The film obtained by curing has heat resistance, electrical properties, mechanical properties, It has been found that this is a polyimide film having excellent adhesiveness to polyimide. That is, the present invention provides (A) a general formula (1):

[0006]

Embedded image [In the formula, X is the formula (2-1), (2-2), (2-3)
And (2-4):

[0007]

Embedded image Y is a divalent aromatic group containing a methacryloxy group represented by the following formula (3):
00 mol% and the divalent aromatic group 7 represented by the following formula (4)
0 to 0 mol%,

[0008]

Embedded image

(In the formula (3), R is the formula (5): -NH-CH ₂ CH ₂ OCO-CH (CH ₃ ) = CH ₂ (5) a group selected from a methacryloyl group-containing group and a hydroxyl group represented by (5), and at least 50 mol% of R is a group represented by the formula (5). In the formula (4), B is represented by the formulas (6-1), (6-2) and (6-3):

[0010]

Embedded image Selected from the groups represented by ) Z is the formula (7):

[0011]

Embedded image

Wherein b is an integer of 5 to 80, and m and n are integers, and m / (m + n) is 0.70 to 0. .98. And a mean molecular weight of 500
The present invention provides a photosensitive resin composition comprising 100 parts by weight of a polyimide resin of 0 to 150,000 and (B) 0.01 to 20 parts by weight of a photopolymerization initiator.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the composition of the present invention will be described in detail. (A) Polyimide resin In the general formula (1) representing the polyimide resin used as the component (A), the tetravalent group represented by X is represented by the formula (2-
Any of 1) to (2-4) may be used, and two or more kinds may be mixed. In the divalent group represented by Y, the methacryloyl group-containing group of the formula (3) is essential, and accounts for 30 to 100 mol%, preferably 50 to 100 mol% of Y. When the group of formula (3) is less than 100 mol%, the remaining groups are groups of formula (4). 30 mol% of the group of the formula (3)
If it is less than 3, the exposed portion does not show sufficient photocurability, and a good pattern cannot be obtained.

In the group of the formula (3), R is a methacryloyl group-containing group of the above formula (5) or a hydroxyl group, provided that the group of the formula (5) is at least 50 mol%, preferably 80 to 10%.
0 mol%.

The groups represented by B are represented by the formulas (6-1) to (6-
One selected from the groups represented by 3) may be used alone or in combination of two or more. Preferably, it is a group of the formula (6-2). The group represented by Z is a siloxane-containing group of the formula (7), and b in the formula (7) is from 5 to 80, preferably from 8 to
It is an integer of 75. If b is less than 5, the elasticity of the resin film is high, so that it is difficult to apply as a protective film for electronic components such as semiconductor elements. If it exceeds 80, the siloxane component becomes insoluble in the system and the polymerization reaction does not proceed. .

In the general formula (1), the ratio of the number of structural units containing Y (m) to the number of structural units containing Z (n) is such that m is 70 to 98 mol% and n is 2-3
0 mol%. Preferably, m is 80 to 98 mol%,
n is 20 to 2 mol%. When m is less than 70 mol%,
The strength of the resin film is reduced and is unsuitable as a protective film. If it exceeds 98 mol%, the adhesion to the substrate is poor. In addition, m is usually 1 to 500 (preferably 3 to 30).
0) and n is 1 to 200 (preferably 1 to 1)
00). This polyimide resin, for example,
It can be manufactured as follows. General formula (8):

[0017]

Embedded image [Wherein, X is as described above]

And an acid anhydride represented by the general formula (9): H ₂ N—Y′—NH ₂ (9) wherein Y ′ is a group represented by the formula (10):

[0019]

Embedded image

It is selected from a divalent aromatic group having a carboxyl group represented by the following formula and a divalent aromatic group represented by the formula (4). And a siloxane diamine compound represented by the general formula (11): H ₂ N—Z—NH ₂ (11) wherein Z is as defined above, according to a conventional method. Synthesize polyimide.

This synthesis may be carried out according to a conventional theory. As the reaction solvent, the same organic solvents as those used in the solution composition of the polyimide resin of the present invention described later, particularly, N-methyl-2-pyrrolidone, cyclohexanone and the like are preferable. Can be used for The reaction is performed by dissolving an acid anhydride and a diamine in a solvent at room temperature (for example, 0 to 40 ° C.) and then reacting to obtain a polyamic acid, and then adding a dehydrating solvent such as toluene and xylene to the reaction solution. Dehydration condensation is performed by heating to about 130 to 200 ° C. to form a polyimide. This is cooled to obtain a polyimide resin. The polyimide resin thus obtained has the formula (1)
2):

[0022]

Embedded image [Wherein X, Y ′, Z, m and n are as described above].

Next, a methacryloyl group is introduced into the carboxyl group of Y ′ in the formula (12) to obtain a resin of the general formula (1). The method of guiding the methacryloyl group is not limited, but is introduced, for example, by reacting isocyanatoethyl methacrylate with the carboxyl group of methylene bis (4-amino-3-benzoic acid). This reaction proceeds at room temperature without a catalyst. At least 50 mol% of R of the resulting resin is a methacryloyl-containing group of the formula (5).

In the above synthesis, the acid anhydride of the general formula (8) is one selected from four compounds having different Xs.
Species or two or more species can be used so as to obtain a desired polyimide structure. The diamine compound of the general formula (9) is used such that the ratio of the group of the general formula (3) to the group of the general formula (4) in the divalent group Y becomes a desired value.
The siloxane group-containing diamine compound of the general formula (11)
The use ratio with other diamine components is adjusted so as to obtain a desired m / (m + n) value.

The diamine compound forming the group of the general formula (3) includes, for example, methylenebis (4-amino-3-
Benzoic acid), methylene bis (4-amino-
2-benzoic acid), methylene bis (3-amino-4-benzoic acid) and the like.

Examples of the diamine compound forming the group of the formula (4) include 1,4-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy)
Benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane, but are not limited thereto. is not. Preferably, it is 2,2-bis [4- (4-aminophenoxy) phenyl] propane.

(B) Photopolymerization Initiator Specific examples of the photopolymerization initiator include the following, but are not limited thereto. Benzophenone, acetophenone, anthrone, phenanthrene, nitrofluorene, ditroacenaphthene, p, p '
-Tetramethyldiaminobenzophenone, p, p'-
Tetraethyldiaminobenzophenone, chlorothioxanthone, benzanthraquinone, 2,6-bis- (4-
Diethylaminobenzal) -cyclohexanone, 2,6
-Bis- (4-diethylaminobenzal) -4-methyl-cyclohexanone, 4,4'-bis- (diethylamino) chalcone, 2,4-diethylthioxanthone, N-
Phenyl-diethanolamine, diethylaminoethyl methacrylate, coumarin compound benzyl, benzoin isopropyl ether, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl- [4- (methylthio) phenylco-2-morpholino-1-propane,
-Phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, N-phenylglycine, 3-phenyl5-isoxazolone, camphorquinone, bimidazoles These may be used alone or in combination of two or more. Can be. The component (B) is a resin 1 of the component (A).
It is used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight.

Other Components The components of the composition of the present invention are usually dissolved in an organic solvent and applied to a substrate in a solution state (as a polyimide resin solution composition). As the solvent used, a solvent used for synthesizing a polyimide precursor is suitably used. Specific examples thereof include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, hexamethylphosphoramide, tetrahydrofuran, 1,4-dioxane, methylcellosolve, butylcellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether. , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone,
2-heptanone, 2-octanone, 7-butyrolactone, butyl cellosolve acetate, toluene, xylene, anisole, methylanisole, ethylphenyl ether and the like, and one of these can be used alone or in combination of two or more. it can. The amount of the solvent used is preferably 5 to 50% by weight of the polyimide resin of the component (A) based on the total amount of the polyimide resin of the component (A) and the solvent.

Method of Use / Use The composition of the present invention is usually used in the above-mentioned solution state by a known method such as spin coating, immersion, and printing.
It is applied to Examples of the substrate include a silicon wafer, a metal plate, a glass sheet, a ceramic substrate, and the like. After the application, use a heating means such as a drier or a hot plate to
Prebake at a temperature of ~ 180 ° C for several minutes to several hours,
By removing most of the solvent in the coating film, a film of the photosensitive resin composition can be obtained. Place a mask on this coating, irradiate light such as visible light, ultraviolet light for several seconds to several minutes,
Next, by dissolving and removing the unexposed portion with a developer,
A relief pattern can be obtained. As the developer used at this time, the above-mentioned solvent used as the solvent for the composition can be used alone or in combination of two or more. Furthermore, since the resin of the relief pattern formed by the development is already in the form of an imidized resin, the resin is heated to 150 to 250 ° C., particularly 150 to 20 ° C. by a heating means such as a dryer or an electric furnace.
By heating at a temperature of 0 ° C. for several tens of minutes to several hours, a patterned polyimide film can be formed only by dispersing the residual solvent, the sensitizer, and the polymerization initiator.

The photosensitive resin composition of the present invention can easily form a pattern, and the resin film formed after heating is excellent in heat resistance, mechanical properties, and electrical properties. It can be suitably used as a protective film. As the protective film for electronic parts, for example, a semiconductor device, specifically, a diode, a transistor, an IC, an L
Junction coating film on the surface of semiconductor devices such as SI,
Α-ray shielding film such as passivation film, buffer coat film, LSI, etc., interlayer insulation film of multilayer wiring, conformal coat of printed circuit board, alignment film of liquid product display element, ion implantation mask, etc. Can be used over a range.

[0031]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples. Synthesis Example 1 44.42 g (0.100 mol) of 2,2-bis (3,4-benzenedicarboxylic acid anhydride) perfluoropropane was placed in a flask equipped with a stirrer, thermometer, nitrogen purge device and ester adapter. And 250 g of cyclohexanone as a solvent. While stirring this solution, 27.00 g of a siloxane-containing diamine having b of 9.8 in the formula (11) was added from a dropping funnel.
(0.030 mol) was added dropwise, followed by 20.02 g (0.07 mol) of methylenebis (4-amino-3-benzoic acid) dissolved in 100 g of cyclohexanone.
0 mol) was added dropwise. After completion of the dropwise addition, stirring was continued for another 10 hours. Thereafter, 50 g of toluene was added to the reaction solution,
The system was heated to 150C. At this time, 3.5 g of water was recovered through an ester adapter. After the completion of the heating, the resultant was cooled to room temperature to obtain a desired resin solution having a structure represented by the following formula (13).

[0032] was observed IR spectrum of the resin, the absorption based on imide group in the 1780 cm ^-1 and 1720 cm ^-1, also absorption derived from phenolic groups in the vicinity of 3300 cm ^-l was observed. Its molecular weight was measured by gel permeation chromatography using tetrahydrofuran as a solvent, and the weight average molecular weight was 45,000 in terms of polystyrene.

[0033]

Embedded image X:

[0034]

Embedded image Y:

[0035]

Embedded image Z:

[0036]

Embedded image

280 g of the resin solution thus obtained
Was charged into a flask, and 8.65 g of isocyanatoethyl methacrylate was added dropwise thereto at room temperature. During the dropping, the temperature of the solution rose, and generation of carbon dioxide gas was observed. After completion of the dropwise addition, the mixture was further stirred at room temperature for 4 hours to introduce a methacryloyl group into the resin (introduced into 50 mol% of -COOH), and to obtain a solution of the resin corresponding to the desired component (A) of the present invention. (Referred to as "a-1"). (Resin solid content about 24% by weight)

[Synthesis Example 2] As a raw material or the like, tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride 8.83 g (0.030 mol)
And 1,3-bis (3,4-dicarboxyphenyl)-
29.82 g (0.070 mol) of 1,1,3,3-tetramethyldisiloxane dianhydride, N as a solvent
-Methyl-2-pyrrolidone 250 g, methylene bis (4-amino-3-benzoic acid) 14.3 g (0.050 mol), 13.3-g 1,3-bis (3-aminophenoxy) benzene as aromatic diamine (0.
045 mol), and 28.62 g (0.005 mol) of a siloxane-containing diamine in which b in the formula (11) is 75, and N-methyl-2-pyrrolidone 110 as a solvent.
g (total 360 g), except that a resin solution having an average molecular weight of 82,000 was obtained in the same manner as in Synthesis Example 1. Isocyanatoethyl methacrylate is added to the resin solution.
A methacryloyl group was introduced using 5 g (-COOH
100 mol% based on the total). Thus, (A) of the present invention
A solution of a resin corresponding to the component (referred to as a-2) was obtained.

Synthesis Example 3 15.51 g (0.050 mol) of 4,4′-oxyphthalic anhydride as tetracarboxylic dianhydride as a raw material, and 1,3
-Bis (3,4-dicarboxyphenyl) -l, 1,
3,3-tetramethyldisiloxane dianhydride 2
1.30 g (0.050 mol), 255 g of cyclohexanone as a solvent, methylene bis (4-amino-3benzoic acid) 11.44 as an aromatic diamine
g (0.040 mol), 16.42 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (0.4 g).
04 mol), and 16.20 g (0.018 mol) of a siloxane-containing diamine in which b is 9.8 in the formula (11), and 11.45 g (0.002 g) of a siloxane diamine in which b is 75 in the formula (11). Mol), and a solution of a resin having an average molecular weight of 23,000 was obtained in the same manner as in Synthesis Example 1 except that 100 g of N-methyl-2-pyrrolidone was used as a solvent. A methacryloyl group was introduced into this resin by using 12.4 g of isocyanatoethyl methacrylate (100 mol% with respect to -COOH). The solution of the resin corresponding to the component (A) of the present invention thus obtained (a-
3).

Synthesis Example 4 32.23 g (0.100 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as an acid anhydride as a raw material and N-methyl as a solvent 250 g of 2-pyrrolidone, 14.3 g (0.050 mol) of methylene bis (4-amino-3-benzoic acid) as an aromatic diamine,
8.91 g of 4,4'-methylenedianiline (0.04
5 mol) and 28.62 g (0.005 mol) of a siloxane-containing diamine wherein b is 75 in the formula (11);
As a solvent, N-methyl-2-pyrrolidone 110 g
A polyimide resin solution having an average molecular weight of 60,000 was obtained in the same manner as in Synthesis Example 1 except that (total 360 g) was used. A methacryloyl group was introduced into this resin solution using 15.5 g of isocyanatoethyl methacrylate (−
100 mol% based on COOH). The resin solution thus obtained is referred to as (a-4).

[Synthesis Example 5] 44.42 g (0.1%) of 2,2-bis (3,4-benzenedicarboxylic anhydride) perfluoropropane as an acid anhydride as a raw material or the like
00 mol) and cyclohexanone 250 as a solvent.
g, 27.00 g (0.030 mol) of siloxane diamine wherein b is 98 in the formula (11), methylene bis (4-amino-3-benzoic acid) 20.0
2 g (0.070 mol), and cyclohexanone 10
A polyimide resin solution having an average molecular weight of 45,000 was obtained in the same manner as in Example 1 except that 0 g was used. To this resin solution, 6.51 g of isocyanatoethyl methacrylate was used to introduce a methacryloyl group (30 mol% based on -COOH). The resin solution obtained in this manner was (a-
5).

Synthesis Example 6 44.42 g (0.100 mol) of 2,2-bis (3,4-benzenedicarboxylic anhydride) perfluoropropane as an acid anhydride, 250 g of cyclohexanone and methylene bis (4 -Amino-3-benzoic acid) 17.1
6 g (0.060 mol), and in the formula (11), b is 75
228.96 g of siloxane diamine (0.04
0 mol) and 100 g of cyclohexanone. However, only a non-uniform yellow-white cloudy solution was obtained, and a uniformly polymerized polyimide resin solution was not obtained.

Examples 1 to 6 and Comparative Examples 1 to 2 As shown in Table 1, a photopolymerization initiator was shown in 100 parts of any of the resin solutions obtained in the synthesis examples in each example. The composition was prepared by adding an amount. The obtained composition was applied to a silicon wafer using a spin coater, and dried on a hot plate at 90 ° C./4 minutes. A photomask having a stripe pattern was brought into close contact with the obtained coating film, and irradiated with ultraviolet light from a 250 W ultra-high pressure mercury lamp for 60 seconds. Next, N
Developed with a solution of -methyl-2-pyrrolidone / xylene = 50/50 for 30 seconds, and rinsed with xylene.

The photosensitivity was evaluated by observing the shape of the obtained line and space pattern and the obtained minimum line width. Further, the obtained pattern was cured in a dryer at 150 ° C./0.5 hours and 200 ° C./1 hour, and then left in a 2 atm pressure cooker for 24 hours to check the adhesion to the wafer. It was examined by an eye peel test (JIS 5400).

The results are shown in Table 1.

[0046]

[Table 1] (Note) α: Ethyl 4-diethylaminobenzoate β: Diethylaminoethyl methacrylate γ: 2,6-bis (4-diethylaminobenzal) -4
-Methylcyclohexanone δ: carbonylbis (diethylaminocoumarin) ε: N-phenylglycine ζ: 3-phenyl5-isoxazolone η: 2,2-bis (o-chlorophenyl) -4,5
4 ', 5'-tetraphenyl-1,2'-biimidazole

As is clear from the results in Table 1, Example 1
The solutions of the resin compositions (1) to (4) have good photosensitivity even in a relatively thick film, give a good pattern after development, and have excellent adhesion to a silicon wafer by heat treatment at a low temperature. A film having properties was formed.

[0048]

As described above, the solution of the photosensitive resin composition of the present invention has excellent storage stability, good sensitivity, and can be easily patterned by a low-temperature heat treatment. To give a cured resin film. Furthermore, this patterned film is made of a polyimide resin having excellent heat resistance, electrical and mechanical properties, and adhesion to a substrate, and can be suitably used as a protective film for electronic components.

Claims (1)

[Claims] (A) General formula (1): [In the formula, X is the formula (2-1), (2-2), (2-3)
And (2-4): Y is a divalent aromatic group containing a methacryloxy group represented by the following formula (3):
00 mol% and the divalent aromatic group 7 represented by the following formula (4)
0 to 0 mol%, (In the formula (3), R is formula _{(5): -NH-CH 2} CH 2 OCO-CH (CH 3) = CH 2 (5) a group selected from a methacryloyl group-containing group and a hydroxyl group represented by (5), and at least 50 mol% of R is a group represented by the formula (5). In the formula (4), B is represented by the formulas (6-1), (6-2) and (6-3): Selected from the groups represented by Z is represented by the formula (7): (Where b is an integer of 5 to 80), and m and n are integers,
m / (m + n) is in the range of 0.70 to 0.98. ]
Having a structure represented by the following formula, and having an average molecular weight of 5,000 to 150,
A photosensitive resin composition comprising 100 parts by weight of a 2,000 polyimide resin and 0.01 part by weight to 20 parts by weight of a photopolymerization initiator (B).