JP3449856B2 - Positive photosensitive resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 as a surface protective film and an interlayer insulating film of semiconductor elements. Due to high integration of elements, large size, thinning and miniaturization of encapsulation resin package, transition to surface mounting method by solder reflow, etc., there is a demand for significant improvement in heat cycle resistance, heat shock resistance, etc. Polyimide resins have become needed. On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has recently been drawing attention, and for example, as the photosensitive polyimide resin, there is the following formula (3).

[Chemical 6]

If 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 are problems in safety and handling. Therefore, recently, a positive type photosensitive resin which can be developed with an alkaline aqueous solution has been developed. For example, Japanese Patent Publication No. 1-46862 discloses a positive photosensitive resin composed of a polybenzoxazole precursor and a diazoquinone compound. In addition to high heat resistance and easy processability, it has excellent electrical properties such as low dielectric constant, fine processability, and sensitivity, and has the potential as a resin for interlayer insulation as well as for wafer coating. There is. The positive type photosensitive resin, in order to perform with an alkaline aqueous solution to remove the Biahoru part, work safety without the need for organic solvents as in the other conventional photosensitive polyimide resin is further improved. However, this photosensitive polybenzoxazole precursor has poor adhesion to a substrate, especially a silicon wafer, and also has a serious defect that the resin is peeled off 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 to improve the adhesion, the problem cannot be completely solved, and the use thereof is currently severely limited.

[0004]

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

[0005]

The present invention is based on the general formula (1)
And 100 parts by weight of the polyamide (A) represented by the formula (1) and 1 to 100 parts by weight of the photosensitive diazoquinone compound (B) and the general formula (2).
A positive type photosensitive resin composition comprising 0.1 to 20 parts by weight of an organosilicon compound (C) represented by

[Chemical 7]

[0006]

[Chemical 8]

The polyamide of the formula (1) is composed of bisaminophenol having a structure of X and dicarboxylic acid having a structure of Y, and when the polyamide is heated at about 300 to 400 ° C., the ring is closed to form a heat-resistant polybenzoxazole. Change to resin. X of the polyamide (1) of the present invention is, for example,

[Chemical 9] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 10] It is more selected.

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

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

Of these, particularly preferred are:

[Chemical 12] It is more selected.

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

[Chemical 13] However, the present invention is not limited to these.

Z in the formula (1) is used when, for example, a substrate such as a silicon wafer is required to have a particularly high adhesiveness, the use ratio b is 40.0 mol% at maximum.
Can be used up to. When it exceeds 40.0 mol%, the solubility of the resin is extremely lowered, scum occurs, and pattern processing cannot be performed. In addition, when using these X, Y, and Z, one kind or a mixture of two or more kinds 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
It is a substance known from No. 3, No. 3,669,658. For example, the following may be mentioned.

[Chemical 14]

[0014]

[Chemical 15]

Among these, the following are particularly preferable.

[Chemical 16]

The photosensitive diazidoquinone compound (B) is compounded in the polyamide (A) in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the polyamide. If the amount is less than 1 part by weight, the patterning property of the resin is poor. On the other hand, if the amount exceeds 100 parts by weight, the tensile elongation of the film is significantly reduced.

If desired, a dihydroxypyridine derivative may be added to the positive photosensitive resin composition of the present invention in order to enhance the photosensitivity. 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-di-carbomethoxy-1,
4-dihydropyridine etc. can be mentioned.

In the positive photosensitive resin composition of the present invention, it is important to further contain the organosilicon compound represented by the general formula (2).

[Chemical 17]

Organosilicon compounds represented by the general formula (2) are represented by US Pat. Nos. 3,755,354 and 4,460,739.
In the present invention, when the organosilicon compound is added to a photosensitive polybenzoxazole precursor as disclosed in Japanese Patent Publication No. 1-46862, a silicon wafer is obtained. On the other hand, it has been found that high adhesion that cannot be obtained with conventional silane coupling agents and 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, N- (2-aminoethyl ) −
Examples thereof include 3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane. Examples of the acid anhydride include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, and the like. One of these may be used alone or two or more of them may be used in combination. Can be used. The compounding 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 with respect to 100 parts by weight of the polyamide (A). If the blending amount is less than 0.1 part by weight, sufficient adhesion to the substrate cannot be obtained, and 2
If the amount exceeds 0 parts by weight, the film loss during development becomes large, which is not preferable.

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 to form a varnish for use.
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, 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, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic or an aluminum substrate. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after prebaking at 60 to 120 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic rays. As the actinic rays, X rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. Next, the irradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di-n. -Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt, and an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol and a surfactant are added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring and obtain a final pattern having high heat resistance. The positive photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also for interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films and the like.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 * Synthesis of polyamide 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane (36.6 parts by weight, 0.100 mol) was dissolved in N, N-dimethylacetamide (150 parts by weight) and pyridine (33.2, 0.420 mol). 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.
Was added dropwise at −10 to −15 ° C. over 30 minutes and then stirred at room temperature for 4 hours to complete the reaction. After filtering the reaction mixture, the solution is poured into water and represented by the general formula (I) of interest,
Polyamide (A ₁ ) consisting of a = 100 and b = 0, where X is a mixture of the following formula X-1 and Y is a mixture of the following formulas Y-1 and Y-2, was precipitated. The precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum at 80 ° C. for 24 hours.

Preparation of positive photosensitive resin composition 100 parts by weight of synthesized polyamide (A ₁ ), 25 parts by weight of diazoquinone (Q1) having the structure of the following formula, organosilicon compound having the structure of the following formula (S- 1) 5 parts by weight of N
-Dissolved in 200 parts by weight of methyl-2-pyrrolidone,
A photosensitive resin composition was obtained by filtering through a 0.2 μm Teflon filter.

* Characteristic Evaluation This photosensitive varnish was applied on a silicon wafer using a spin coater and then dried in an oven at 70 ° C. for 1 hour to obtain a coating film having a thickness of about 6 μm. Letterpress printing on this coating
Mask (Test Chart No. 1; width 50-0.
After irradiating the ultraviolet ray from the high pressure mercury lamp through the 88 μm remaining pattern and the blank pattern),
The exposed portion was dissolved and removed by immersion in a 0.79% tetramethylammonium hydroxide aqueous solution 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 blank pattern was resolved on the silicon wafer. The film thickness after development at this time was 5.1 μm, and the residual film ratio (film thickness after development / film thickness before development × 10
0) was 85.0%. Separately, a photosensitive varnish was applied on a silicon wafer in the same manner and prebaked, and then in an oven for 30 minutes / 150 ° C., 30 minutes / 250 ° C.,
The resin was cured by heating in the order of 30 minutes / 350 ° C.
The obtained coating film was cut into 1 mm square and 100 pieces were cut on a substrate, peeled off with a cellophane tape, and the coating film was tried to be peeled off from the silicon wafer. It was confirmed that the adhesion of the cured film to the wafer was excellent. Furthermore, this silicon wafer was heated at 125 ° C. for 2.3 at.
After 100 hours of precooker cooker (PCT) treatment of m, cellophane tape was similarly attached and peeled off and evaluated. The number of peeled coating films (this is called "the number of peelings after high temperature and high humidity treatment") ) Was 0, and it was confirmed that the adhesion after the high temperature and humidity treatment was also excellent.

Example 2 The organosilicon compound in Example 1 was replaced with the following formula S-2 for evaluation. << Example 3 >> The organosilicon compound in Example 1 was replaced with the following formula S-3 for evaluation. << Example 4 >> The organosilicon compound (S-
Evaluation was carried out using 1 part by weight of the addition amount of 1). << Example 5 >> 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 the compound was represented by the general formula (1), and X was represented by the following formula. X-
A polyamide (A ₂ ) in which 1 and Y are the following formula Y-3 and a = 100 and b = 0 was synthesized, and otherwise, the same evaluation as in Example 1 was performed.

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 was used, and 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane was replaced with 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to give a compound of the general formula (1)
, X is the following formula X-2, Y is the following formula Y-3, and a
= 100 and b = 0, a polyamide (A ₃ ) was synthesized, and otherwise the same evaluation as in Example 1 was performed. << Example 7 >> In the synthesis of the polyamide in Example 1, diphenyl ether-4,4'-dicarboxylic acid chloride was used in place of terephthalic acid chloride and isophthalic acid chloride, and 2,2-bis (3-amino-4) was used. -Hydroxyphenyl) hexafluoropropane is used in place of 3,3'-diamino-4,4'-dihydroxydiphenyl ether, and is represented by the general formula (1), X is the following formula X-3, and Y is the following formula. In Y-3, a = 100, b =
A polyamide (A ₄ ) consisting of 0 was synthesized, and a diazoquinone (Q2) having the following structure was used as the diazoquinone to obtain a photosensitive resin composition. Others were evaluated in the same manner as in Example 1. Example 8 In the synthesis of the polyamide in Example 1, 3,4.8 parts by weight of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.0
95 mol) and replaced by 1.24 parts by weight (0.005 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (1) ), 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, and a = 95, b
A polyamide (A ₅ ) having a number of ₅ was synthesized, and otherwise the same evaluations as in Example 1 were performed.

Comparative Example 1 Evaluation was carried out in Example 1 without adding the organosilicon compound. << Comparative Example 2 >> Evaluation was carried out in Example 5 without adding the organosilicon compound. << Comparative Example 3 >> Evaluation was carried out in Example 6 without adding the organosilicon compound. << Comparative Example 4 >> The evaluation was performed by reducing the addition amount of the organosilicon compound in Example 1 to 0.5 part by weight. << Comparative Example 5 >> The amount of the organosilicon compound added in Example 1 was increased to 50 parts by weight for evaluation. << Comparative Example 6 >> The organosilicon compound of Example 1 was replaced with S-
Evaluation was carried out in place of 4. << Comparative Example 7 >> The organosilicon compound of Example 1 was replaced with S-
Evaluation was carried out in place of 5. << Comparative Example 8 >> The organosilicon compound in Example 1 was replaced with S-
Evaluation was carried out in place of 6. Above Examples 1 to 8 and Comparative Example 1
Table 1 shows the evaluation results of ~ 8.

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

[0031]

[Chemical 21]

[0032]

[Table 1]

[0033]

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

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/037 G03F 7/037 (56) References JP-A-8-123034 (JP, A) JP-A-8-22118 (JP , A) JP-A-7-281441 (JP, A) JP-A-4-346993 (JP, A) JP-A-60-49077 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) G03F 7/00-7/42

Claims (5)

(57) [Claims] 1. 100 parts by weight of polyamide (A) represented by general formula (1) and 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 the organosilicon compound (C) represented by the general formula (2). [Chemical 1] [Chemical 2] 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 a positive photosensitive resin composition according to claim 1 or 2, selected from the following. [Chemical 3] 4. Y in the polyamide of general formula (1)
The positive photosensitive resin composition according to claim 1, 2 or 3, selected from the following. [Chemical 4] 5. The positive-type photosensitive resin composition according to claim 1, 2, 3 or 4, wherein the photosensitive diazoquinone compound (B) is selected from the following. [Chemical 5]