JPH1010727A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. having superior adhesion to a substrate by incorporating specified polyamide, a photosensitive diazoquinone compd. and a specified organosilicon compd. SOLUTION: This photosensitive resin compsn. consists of 100 pts.wt. polyamide represented by formula I, 1-100 pts.wt. photosensitive diazoquinone compd. and 0.1-20 pts.wt. organosilicon compd. represented by formula II. In the formula I, X is a tetravalent arom. group, Y is a divalent arom. group and Z is a group represented by formula III, wherein each of R1 and R2 is a divalent org. group, each of R3 and R4 is a monovalent org. group, a+b=100mol%, (a) is 60-100mol% and (b) is 0-40mol%. In the formula II, R5 is a divalent arom. residue or a divalent org. group, R6 is a divalent org. group, each of R7 and R8 is a monovalent org. group, R7 and R8 may be different from each other and (l) is 0, 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition having excellent adhesion to a substrate.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used for a surface protective film and an interlayer insulating film of a semiconductor element. There is a demand for remarkable improvement in heat cycle resistance and heat shock resistance due to the high integration and large size of the elements, the thinning and miniaturization of the sealing resin package, and the shift to the surface mounting method by solder reflow. Is required. On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has recently attracted attention. For example, the following formula (3) is given as a photosensitive polyimide resin.

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When this is used, a part of the pattern forming process can be simplified and the process can be shortened.
Since a solvent such as methyl-2-pyrrolidone is required, there is a problem in safety and handling. Therefore, recently, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been developed. For example, Japanese Patent Publication No. 1-46862 discloses a positive photosensitive resin comprising a polybenzoxazole precursor and a diazoquinone compound. It has excellent electrical properties such as low dielectric constant, fine workability and sensitivity in addition to high heat resistance and easy workability, and has the potential not only as a wafer coat application but also as a resin for interlayer insulation. I have. This positive photosensitive resin does not require an organic solvent unlike other conventional photosensitive polyimide resins because the via hole portion is removed using an alkaline aqueous solution, so that the work safety is further improved. However, this photosensitive polybenzoxazole precursor has poor adhesion to a substrate, particularly a silicon wafer, and also has a serious defect that the resin is separated from the substrate by a high-temperature moisture absorption treatment after curing.
Therefore, even if a commercially available silane coupling agent or the like is added for the purpose of improving the adhesion, the problem cannot be completely solved, and at present, its use is severely restricted.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive photosensitive resin having excellent adhesion to a substrate.

[0005]

According to the present invention, there is provided a compound represented by the general formula (1):
And 100 to 100 parts by weight of a photosensitive diazoquinone compound (B) represented by the formula (2):
A positive photosensitive resin composition comprising 0.1 to 20 parts by weight of an organosilicon compound (C) represented by the formula:

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[0006]

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The polyamide of the formula (1) comprises bisaminophenol having the structure of X and dicarboxylic acid having the structure of Y. When the polyamide is heated at about 300 to 400 ° C., the ring is closed, and the heat resistance of polybenzoxazole is obtained. Changes to resin. X of the polyamide (1) of the present invention is, for example,

Embedded image Etc., but are not limited to these.

[0008] Of these, particularly preferred are:

Embedded image It is more chosen.

Further, Y in the formula (1) is, for example,

Embedded image Etc., but are not limited to these.

[0010] Of these, particularly preferred are:

Embedded image It is more chosen.

Further, Z in the equation (1) is, for example,

Embedded image Etc., but are not limited to these.

Z in the formula (1) is used, for example, when adhesion is particularly required to a substrate such as a silicon wafer.
Can be used up to. If it exceeds 40.0 mol%, the solubility of the resin is extremely reduced, scum is generated, and pattern processing cannot be performed. When using X, Y, and Z, one type or a mixture of two or more types may be used.

The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is disclosed in US Pat. Nos. 2,772,972 and 2,797, 21
No. 3,669,658. For example, the following are mentioned.

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[0014]

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Among these, the following are particularly preferred.

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The compounding amount of the photosensitive diazidoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide. If the compounding amount is less than 1 part by weight, the patterning property of the resin is poor. Conversely, if it exceeds 100 parts by weight, the tensile elongation of the film is significantly reduced.

A dihydroxypyridine derivative can be added to the positive photosensitive resin composition of the present invention, if necessary, to enhance the photosensitive characteristics. Examples of the dihydroxypyridine derivative include 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine and 4- (2'-nitrophenyl) -2,6
-Dimethyl-3,5-dicarbethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl)
-2,6-dimethyl-3,5-carbomethoxy-1,4
-Dihydropyridine and the like.

It is important that the positive photosensitive resin composition of the present invention further contains an organosilicon compound represented by the general formula (2).

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The organosilicon compounds represented by the general formula (2) are disclosed in US Pat. Nos. 3,755,354 and 4,460,739.
In the present invention, this organosilicon compound is added to a photosensitive polybenzoxazole precursor as shown in Japanese Patent Publication No. 1-46862, and is known in the art. On the other hand, it has been found that a high adhesiveness that cannot be obtained with a conventional silane coupling agent or the like can be exhibited. The organosilicon compound represented by the general formula (2) can be obtained by reacting a silicon compound having an amino group with an acid anhydride. Examples of the silicon compound having an amino group include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl )-
Examples thereof include 3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane. Examples of the acid anhydride include, for example, maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, and the like.One of these may be used alone, or two or more may be used in combination. Can be used. The amount of the organosilicon compound represented by the general formula (2) in the positive photosensitive resin composition is 0.1 to 20 parts by weight based on 100 parts by weight of the polyamide (A). If the amount is less than 0.1 part by weight, sufficient adhesion to the substrate cannot be obtained.
If the amount exceeds 0 parts by weight, the film loss during development is undesirably large.

If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition of the present invention. In the present invention, these components are dissolved in a solvent and used in the form of a varnish.
Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3
-Butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and the like may be used alone or in combination.

In the method of using the positive photosensitive resin composition of the present invention, the composition is first applied to a suitable support, for example, a silicon wafer, ceramic, aluminum substrate or the like. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after pre-baking at 60 to 120 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like 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 irradiated portion with a developer. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and quaternary ammoniums such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a salt or an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant thereto can be suitably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing liquid. Next, heat treatment is performed to form an oxazole ring, and a final pattern having high heat resistance is obtained. The positive photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as interlayer insulation for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like.

[0022]

The present invention will be described below in detail with reference to examples. << Example 1 >> * Synthesis of polyamide 2,2-bis (3-amino-4-hydroxyphenyl)
36.6 parts (0.100 mol) of hexafluoropropane were dissolved in 150 parts by weight of N, N-dimethylacetamide and 33.2 (0.420 mol) of pyridine. Next, 17.0 parts by weight (0.084 mol) of terephthalic acid chloride and 4.3 parts by weight (0.021 mol) of isophthalic acid chloride dissolved in 100 parts by weight of cyclohexanone were used.
Was added dropwise at -10 to -15 ° C over 30 minutes, followed by stirring at room temperature for 4 hours to complete the reaction. After the reaction mixture is filtered, the solution is poured into water and represented by the desired general formula (I):
X is a mixture of the following formulas X-1 and Y is a mixture of the following formulas Y-1 and Y-2 to precipitate a polyamide (A ₁ ) consisting of a = 100 and b = 0. The precipitate was collected by filtration, washed sufficiently with water, and then dried at 80 ° C. under vacuum overnight.

* Preparation of Positive Photosensitive Resin Composition 100 parts by weight of the synthesized polyamide (A ₁ ), 25 parts by weight of diazoquinone (Q1) having a structure of the following formula, and an organosilicon compound (S- 1) 5 parts by weight of N
-Methyl-2-pyrrolidone after dissolving in 200 parts by weight,
The mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive resin composition.

* Characteristic evaluation The photosensitive varnish was applied on a silicon wafer by using a spin coater, and then dried in an oven at 70 ° C. for 1 hour to obtain a coating having a thickness of about 6 μm. Letterpress printing on this coating
Co., Ltd. mask (test chart No. 1; width 50 to 0.
After irradiating ultraviolet light from a high-pressure mercury lamp through
The exposed portion was dissolved and removed by immersion in a 0.79% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and then the developing solution was rinsed with pure water for 30 seconds (rinse).
As a result, it was confirmed that a 5 μm punch pattern was resolved on the silicon wafer. At this time, the film thickness after development was 5.1 μm, and the residual film ratio (film thickness before development / film thickness before development × 10
0) was 85.0%. Separately, a photosensitive varnish was similarly applied on a silicon wafer, and after prebaking, 30 minutes / 150 ° C., 30 minutes / 250 ° C. in an oven.
The resin was heated in the order of 30 minutes / 350 ° C. to cure the resin.
The obtained coating film was cut into 100 squares on a 1 mm square, a cellophane tape was stuck, peeled off, and the coating film was peeled off from the silicon wafer. (Referred to as “post-peeling number”) was 0, and it was confirmed that the cured film had excellent adhesion to the wafer. Further, this silicon wafer was heated at 125 ° C. and 2.3 at.
m after a 100-hour pre-shear cooker (PCT) treatment, a cellophane tape was similarly adhered, peeled off, and evaluated. The number of peeled coating films (this is referred to as the “peeling number after high-temperature and high-humidity treatment”) ) Was 0, which confirmed that the adhesion after the high-temperature and humidity treatment was excellent.

Example 2 The evaluation was performed by replacing the organosilicon compound in Example 1 with the following formula S-2. << Example 3 >> The evaluation was performed by replacing the organosilicon compound in Example 1 with the following formula S-3. << Example 4 >> The organosilicon compound (S-
The evaluation was performed by adding 1 part by weight of 1). Example 5 In the synthesis of polyamide in Example 1, diphenyl ether-4,4'-dicarboxylic acid chloride was used instead of terephthalic acid chloride and isophthalic acid chloride, and the general formula (1) was used. X-
1, a polyamide (A ₂ ) having Y = the following formula Y = a = 100 and b = 0 was synthesized, and the other evaluations were performed in the same manner as in Example 1.

Example 6 In the synthesis of polyamide in Example 1, diphenyl ether-4,4'- was used instead of terephthalic acid chloride and isophthalic acid chloride.
Dicarboxylic acid chloride is used and 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane is replaced by 3,3'-diamino-4,4'-dihydroxydiphenylsulfone to give a compound of the general formula (1)
X is the following formula X-2, Y is the following formula Y-3,
= 100, and the synthesis of b = 0 a polyamide (A _3), others were evaluated in the same manner as in Example 1. Example 7 In the synthesis of the polyamide in Example 1, diphenyl ether-4,4'-dicarboxylic acid chloride was used instead of terephthalic acid chloride and isophthalic acid chloride, and 2,2-bis (3-amino-4 -Hydroxyphenyl) hexafluoropropane is replaced by 3,3'-diamino-4,4'-dihydroxydiphenyl ether, represented by the general formula (1), wherein X is the following formula X-3, and Y is the following formula In Y-3, a = 100, b =
Synthesis of a polyamide (A ₄ ) consisting of No. 0 was carried out, and a diazoquinone (Q2) having the following structure was used as the diazoquinone to obtain a photosensitive resin composition. Other evaluations were conducted in the same manner as in Example 1. << Example 8 >> In the synthesis of the polyamide in Example 1, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added with 34.8 parts by weight (0.08 parts by weight).
95 mol), and 1.24 parts by weight (0.005 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added instead. X is the following formula X-1, and Y is the following formula Y-1
And Y-2, Z is the following formula Z-1, a = 95, b
= A five polyamide (A ₅₎ were synthesized, others were evaluated in the same manner as in Example 1.

Comparative Example 1 Evaluation was made in Example 1 without adding an organosilicon compound. << Comparative Example 2 >> Evaluation was made in Example 5 without adding an organosilicon compound. << Comparative Example 3 >> Evaluation was made in Example 6 without adding an organosilicon compound. << Comparative Example 4 >> The evaluation was performed by reducing the amount of the organosilicon compound in Example 1 to 0.5 part by weight. << Comparative Example 5 >> The evaluation was performed by increasing the amount of the organosilicon compound in Example 1 to 50 parts by weight. << Comparative Example 6 >> The organosilicon compound in Example 1 was replaced with S-
The evaluation was performed in place of 4. << Comparative Example 7 >> The organosilicon compound in Example 1 was replaced with S-
The evaluation was performed in place of 5. << Comparative Example 8 >> The organosilicon compound in Example 1 was replaced with S-
The evaluation was performed in place of 6. Examples 1 to 8 and Comparative Example 1
Table 1 shows the evaluation results of Nos. To 8.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

[Table 1]

[0033]

According to the present invention, a positive photosensitive resin composition having excellent adhesion to a substrate can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03F 7/075 501 G03F 7/075 501 // (C08K 5/23 5:54) (72) Invention Person Toshiro Takeda 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd.

Claims (5)

[Claims] 1. 100 parts by weight of a polyamide (A) represented by the general formula (1) and a photosensitive diazoquinone compound (B)
A positive photosensitive resin composition comprising 1 to 100 parts by weight and 0.1 to 20 parts by weight of an organosilicon compound (C) represented by the general formula (2). Embedded image Embedded image 2. The positive photosensitive resin composition according to claim 1, wherein R ₅ in the organosilicon compound (C) represented by the general formula (2) is —CH ＝ CH—. 3. X in the polyamide of the general formula (1)
Is selected from the following: The positive photosensitive resin composition according to claim 1 or 2, wherein Embedded image 4. Y in the polyamide of the general formula (1)
Is selected from the following: The positive photosensitive resin composition according to claim 1, 2 or 3. Embedded image 5. The positive photosensitive resin composition according to claim 1, wherein the photosensitive diazoquinone compound (B) is selected from the following. Embedded image