JP3422704B2 - Positive 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 positive photosensitive resin composition capable of obtaining a highly sensitive pattern having a high residual film ratio and having excellent adhesion to a sealing resin and a substrate.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance and excellent electric characteristics and mechanical characteristics 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, heat shock resistance, etc. due to integration, upsizing, thinning and miniaturization of encapsulation resin package, transition to surface mounting by solder reflow, etc. It has become necessary. On the other hand, a technique of 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 (7).

[0003]

[Chemical 12]

If this is used, a part of the pattern forming process can be simplified and the effect of shortening the process can be obtained.
-Since a solvent such as methyl-2-pyrrolidone is required,
There is a problem in safety and handling. So 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 composed of a polybenzoxazole resin and a diazoquinone compound or a polybenzoxazole precursor and a diazoquinone compound. It has high heat resistance, excellent electrical characteristics, and fine workability, and has potential as a resin for not only wafer coating but also interlayer insulation.

The developing mechanism of this positive type photosensitive resin is that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, and upon exposure, the diazoquinone compound undergoes a chemical change and becomes soluble in the alkaline aqueous solution.
By utilizing the difference in solubility between the exposed portion and the unexposed portion, it becomes possible to create a coating film pattern only in the unexposed portion.

When these photosensitive resins are actually used,
A particular problem is the sensitivity of the photosensitive resin. If the sensitivity is low, the exposure time per wafer becomes long, and the throughput decreases. Therefore, in order to improve the sensitivity of the photosensitive resin, for example, when the molecular weight of the polybenzoxazole resin of the base resin is reduced, the film loss of the unexposed portion at the time of development becomes large, and the pattern shape deteriorates. Although low molecular weight phenols are added to increase sensitivity, high sensitivity
It is necessary to increase the addition amount in order to obtain a high residual film rate, which has a drawback that the storage stability of the varnish is significantly reduced.

Adhesiveness is an important characteristic of such a photosensitive resin. First of all, as the adhesion, the adhesion to a base such as a silicon wafer is important. If the adhesion to the base is poor, the pattern may peel off during development,
After curing, peeling occurs when moisture-proof treatment is performed. Further, the adhesion between the photosensitive resin and the sealing resin molded thereon is also important. Recently, in the trend of smaller and thinner packages and surface mounting, strict quality requirements are demanded. Among them, the adhesiveness between the chip coated with the photosensitive resin and the sealing resin is poor, and peeling occurs at the interface, which makes it practical. There is a problem with the property, and there is a strong demand for a photosensitive resin that is more excellent in adhesiveness with a sealing resin.

[0008]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a positive type photosensitive resin capable of obtaining a pattern having a high sensitivity and a high residual film ratio, and having excellent adhesion to a sealing resin and a substrate. And

[0009]

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).
And 1 to 30 parts by weight of the phenol compound (C) of (3) and 1 to 10 parts by weight of at least one organosilicon compound (D) selected from the general formulas (4), (5) and (6). And a positive photosensitive resin composition.

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

The polyamide of the formula (1) is synthesized from a diamine having a structure of X, a dicarboxylic acid having a structure of Y and a carboxylic acid derivative having a structure of E. When the polyamide is heated at about 300 to 400 ° C. It closes the ring and changes into a heat-resistant resin called polybenzoxazole. X of the polyamide (1) of the present invention is, for example,

[0017]

[Chemical 13]

However, the present invention is not limited to these. Among these, particularly preferable are:

[0019]

[Chemical 7]

It is selected from the above. Further, Y in the formula (1) is, for example,

[0021]

[Chemical 14]

However, the present invention is not limited to these. Among these, particularly preferable are:

[0023]

[Chemical 8]

It is selected from the above. E in equation (1)
Is obtained by reacting a dicarboxylic acid derivative having a structure of Y with a diamine having a structure of X to synthesize a polyamide,
A terminal carboxylic acid derivative having at least one alkenyl group or alkynyl group as a terminal amino group is reacted to perform terminal blocking, and examples of the carboxylic acid derivative include 5-norbornene-2,3-dicarboxylic acid and maleic anhydride. Among them, 5-norbornene-2,3-dicarboxylic acid is particularly preferable. Further, Z in the formula (1) is, for example,

[0025]

[Chemical 15]

However, the present invention is not limited to these. Z in the formula (1) is used, for example, when adhesion is particularly required for a substrate such as a silicon wafer.
With respect to the usage rate b, up to 40.0 mol% can be used. 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 2,797,213.
No. 3,669,658.
For example, the following may be mentioned.

[0028]

[Chemical 16]

[0029]

[Chemical 17]

Among these, the following are particularly preferable from the viewpoint of high residual film ratio.

[0031]

[Chemical 9]

The photosensitive diazoquinone compound (B) is blended 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 exceeds 100 parts by weight, the tensile elongation of the film is remarkably reduced. If necessary, a dihydropyridine derivative may be added to the positive photosensitive resin composition of the present invention in order to enhance the photosensitivity. As the dihydropyridine derivative,
For example, 2,6-dimethyl-3,5-diacetyl-4-
(2'-Nitrophenyl) -1,4-dihydropyridine, 4- (2'-nitrophenyl) -2,6-dimethyl-3,5-dicarboethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl) -2,6-
Dimethyl-3,5-dicarbomethoxy-1,4-dihydropyridine and the like can be mentioned. In the positive photosensitive resin composition of the present invention, the above-mentioned components (A) and (B)
In addition to the above, it is important to further contain the phenol compound (C) represented by the general formulas (2) and (3).

[0033]

[Chemical 2]

[0034]

[Chemical 3]

A technique for adding a phenol compound to a positive resist composition is, for example, JP-A-3-2002.
51, JP-A-3-200252, JP-A-3
-200253, JP-A-3-200254, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, and JP-A-4-123.
56 and JP-A-4-12357. However, the phenol compounds as shown in these have little effect of improving the sensitivity even when used in the positive photosensitive resin having the polyamide as the base resin in the present invention,
In order to improve the sensitivity, it is necessary to increase the added amount, and then the residual film rate is significantly reduced.

However, when the phenol compound represented by the general formula (2) in the present invention is used, the dissolution rate in the exposed area is increased and the sensitivity is improved. In addition, the film loss in the unexposed area, which is observed when the molecular weight is decreased to increase the sensitivity, is very small and good. Further, it has been found that by adding a phenol compound represented by the general formula (2), a positive type photosensitive resin composition having improved adhesiveness with a sealing resin can be obtained as a new property. The phenol compound represented by the general formula (3) is disclosed in JP-A-4-11.
When the polyamide of the present invention is used as a base, it has the effect of improving the sensitivity, but the decrease in the residual film rate is rather large. However, when used in combination with the phenol compound represented by the general formula (2), it is not necessary to increase the addition amount, so that it is possible to suppress the decrease in the residual film rate and improve the sensitivity. Further, there is no precipitation during low temperature storage, which is observed when the addition amount of the phenol compound represented by the general formula (2) is increased, and the storability can be improved. Further, the phenol compound represented by the general formula (3) has a new characteristic similar to that of the phenol compound represented by the general formula (2), and a positive type photosensitive resin composition having improved adhesion to the sealing resin is obtained. I found that I could be. Examples of the compound represented by the general formula (2) include, but are not limited to, the followings.

[0037]

[Chemical 18]

[0038]

[Chemical 19]

[0039]

[Chemical 20]

[0040]

[Chemical 21]

Of these, particularly preferable in terms of sensitivity and residual film ratio are:

[0042]

[Chemical formula 22]

And has the general formula (22-A) or (22-
The compound represented by B) is contained alone or in the form of a mixture in the phenol compound (C) in an amount of 50% by weight or more.

Examples of the phenol compound represented by the general formula (3) used in the present invention include, but are not limited to, the following compounds.

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

The total amount of the phenol compound (C) added is 1 to 3 with respect to 100 parts by weight of the polyamide (A).
0 parts by weight is preferred. If the amount added is less than 1 part by weight, the effect of improving the sensitivity cannot be obtained, and if the amount added exceeds 30 parts by weight, the residual film rate decreases significantly, or precipitation easily occurs during freezing storage. The present invention is characterized in that the phenol compound (D) of the general formula (2) and the general formula (3) is used in combination, but either the general formula (2) or (3) is excessive depending on the required characteristics. By using it, it is possible to make the addition amount with emphasis on the required characteristics.

The organosilicon compounds of the present invention represented by the general formulas (4), (5) and (6) are used for improving the adhesiveness between the photosensitive resin and the base substrate. Although one kind or a mixture of two or more kinds may be used, the organosilicon compound of the present invention represented by the general formula (4) has a general formula ( It is desirable to use 5) or (6) or both (5) and (6) together. The addition amount is preferably 1 to 10 parts by weight with respect to 100 parts by weight of polyamide. If it is less than 1 part by weight, the effect of improving the adhesiveness cannot be obtained, and if it exceeds 10 parts by weight, the mechanical strength of the polybenzoxazole film formed on the semiconductor element is lowered and the stress relaxation effect is weakened. Absent.

The organosilicon compounds represented by the general formulas (4) and (5) are acid anhydride or acid dianhydride and a silane coupling agent having an amino group in an organic solvent at 20 to 100 ° C. for 30 minutes. It can be easily obtained by reacting for 10 hours. Examples of the acid anhydride used include maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic acid, phthalic anhydride, etc. However, it is not particularly limited.

Examples of acid dianhydrides include, for example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and 3,3 ', 4,4'-benzophenone. Tetracarboxylic dianhydride, 2,2 ', 3,3'
-Benzophenone tetracarboxylic 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, 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
-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4
5,8-Tetracarboxylic acid dianhydride, 2,3,6,7-
Tetrachloronaphthalene-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 acid Dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3"-
p-terphenyl tetracarboxylic dianhydride, 2,3
3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl)-
Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, bis (2,2
3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,
8,9-tetracarboxylic dianhydride, perylene-3,
4,9,10-tetracarboxylic dianhydride, perylene-
4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,6,7-Tetracarboxylic acid dianhydride, phenanthrene-1,2,9,1
0-tetracarboxylic dianhydride, pyrazine-2,3,
5,6-tetracarboxylic dianhydride, pyrrolidine-2,
3,4,5-tetracarboxylic dianhydride, thiophene-
2,3,4,5-tetracarboxylic dianhydride, 4,4 '
-Hexafluoroisopropylidene diphthalic acid dianhydride and the like, but not limited thereto.

Examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ
-Aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N -(Β-aminoethyl) -γ-aminopropyltriethoxysilane, N-
(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane and the like.

The organosilicon compound represented by the general formula (6) comprises an epoxy group-containing silane coupling agent and a tetracarboxylic dianhydride at 20 to 100 ° C. for 30 minutes to 10 minutes.
It is easily obtained by reacting for a time. Examples of the acid dianhydride are the same as in the case of the organosilicon compound of the general formula (5), but examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriamine. Ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxy Propyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, and the like. The above general formula (4),
The organosilicon compounds represented by (5) and (6) have been found to have properties by preliminarily reacting, but it is also possible to add the respective raw materials without performing the preliminary reaction.

If necessary, additives such as a leveling agent and a silane coupling agent may 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, the composition is first 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
It 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.

[0057]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 * Synthesis of Polyamide 443.2 g (0.9 mol) of dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4'-dicarboxylic acid with 2 mol of 1-hydroxybenzotriazole and hexa Fluoro-2,2-bis (3-amino-4)
-Hydroxyphenyl) propane 366.3 g (1.0
Mol) and N were placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and N
-Methyl-2-pyrrolidone (3000 g) was added and dissolved. Then, the reaction was carried out at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic acid dianhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the reaction was terminated by further stirring for 12 hours. After filtering the reaction mixture, the reaction mixture was added to a solution of water / methanol = 3/1, the precipitate was aggregated, washed thoroughly with water, and then dried under vacuum to obtain the target polyamide (A1).

Preparation of Positive Photosensitive Resin Composition 100 parts by weight of synthesized polyamide (A1), 25 parts by weight of diazoquinone (Q1) having the structure of the following formula, 10 parts by weight of phenol compound (P1) having the structure of the following formula Department,
(P2) 5 parts by weight, 2 parts by weight of the organosilicon compound (S1) obtained by reacting γ-aminopropyltriethoxysilane with maleic anhydride, γ-aminopropyltriethoxysilane and 4,4′- 1 part by weight of an organosilicon compound (S2) obtained by reacting oxydiphthalic anhydride was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone, and then filtered through a 0.2 μm Teflon filter to form a photosensitive resin composition. I got a thing.

* Characteristic Evaluation This positive photosensitive resin composition was applied onto 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 5 μm. A g-line stepper exposure machine NSR-1505G3A (Nikon
50mJ through a reticle (Reticle)
/ Cm ² from 10 mJ / cm ^{2 in} increments of 540 mJ /
Exposure was performed up to cm ² . Next, the exposed portion was dissolved and removed by immersion in a 1.4% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that the pattern was formed from the irradiated portion with the exposure dose of 200 mJ / cm ² (that is, the sensitivity was 200 mJ / cm ² ). The residual film rate (film thickness after development / film thickness before development) at this time was 90.2%.
And showed a very high value. Separately, a positive type photosensitive resin composition is similarly coated on a silicon wafer and prebaked, and then in an oven for 30 minutes / 150 ° C., 30 minutes / 250.
The resin was cured by heating in the order of 30 ° C. and 30 minutes / 350 ° C.

Furthermore, an epoxy resin composition for semiconductor encapsulation (EME-6300 manufactured by Sumitomo Bakelite Co., Ltd.) was formed on the cured film.
H) was molded into a size of 2 × 2 × 2 mm (horizontal × vertical × height). Using Tensilon, the epoxy resin composition for encapsulation molded on the polybenzoxazole resin cured film was peeled off, and the shear strength was measured. As a result, 4.3 kg / mm ²
Met. Separately, a photosensitive varnish was applied on a silicon wafer in the same manner, prebaked and then placed in an oven.
The resin was cured by heating in the order of min / 150 ° C., 30 min / 250 ° C., 30 min / 350 ° C. Obtained coating film 1 mm
I tried to peel off the coating from the silicon wafer by cutting it into 100 corners on the corner, attaching cellophane tape and peeling it off, but the number of peeled coatings (this is called "the number of peelings after curing") ) Was 0, and it was confirmed that the adhesion of the cured film to the wafer was excellent. Further, this silicon wafer was subjected to a pressure cooker (PCT) treatment at 125 ° C. and 2.3 atm for 100 hours, and then a cellophane tape was attached in the same manner and peeled off for evaluation.
The number of peeled coating films (referred to as "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 phenol compound (P1) in Example 1 was replaced with the following formula (P3), and trial production and evaluation were carried out. Example 3 Phenol compound (P
1) was replaced with the following formula (P4), and trial production and evaluation were performed. Example 4 Phenol compound (P
15 parts by weight of 1), phenol compound (P2)
Trial production and evaluation were performed with the addition amount of 8 parts by weight. Example 5 Phenol compound (P
Trial production and evaluation were carried out with the addition amount of 1) as 1 part by weight and the addition amount of the phenol compound (P2) as 2 parts by weight.

Example 6 In the synthesis of the polyamide in Example 1, 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxybenzotriazole 2 were used.
Instead of the dicarboxylic acid derivative obtained by reacting with mol, diphenylsulfone-4,4′-dicarboxylic acid 1
Polyamide (A2) was synthesized using the dicarboxylic acid derivative obtained by reacting 2 mol of 1-hydroxybenzotriazole with 1 mol, and other trial production and evaluation were performed in the same manner as in Example 1.

Example 7 In the synthesis of the polyamide in Example 1, 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxybenzotriazole 2 were used.
A dicarboxylic acid derivative obtained by reacting 0.8 mol of terephthalic acid, 0.2 mol of isophthalic acid with 2 mol of 1-hydroxybenzotriazole is used instead of the dicarboxylic acid derivative obtained by reacting Polyamide (A3) was synthesized with the same procedure, and other trials and evaluations were performed in the same manner as in Example 1.

Example 8 In the synthesis of the polyamide in Example 1, hexafluoro-2,2-bis (3-
Using 1 mol of 3,3′-diamino-4,4′-dihydroxyphenylsulfone instead of 1 mol of amino-4-hydroxyphenyl) propane, a polyamide (A4) was synthesized, and further diazoquinone of the following formula structure was used. 1 part by weight of an organosilicon compound obtained by using diazoquinone (Q2) to obtain a photosensitive resin composition and reacting γ-aminopropyltriethoxysilane with maleic anhydride instead of the organosilicon compound of Example 1. , 0.5-part by weight of an organosilicon compound obtained by reacting γ-aminopropylethoxysilane with 3,3 ′, 4,4′-benzophenone tetracarbic acid dianhydride (S3), and γ-glycidoxy Propyltrimethoxysilane and 3,3 ', 4,4'
Trial manufacture and evaluation were performed in the same manner as in Example 1 except that 0.5 part by weight of an organosilicon compound obtained by reacting with benzophenonetetracarboxylic dianhydride (S4) was used.

Example 9 In the synthesis of polyamide in Example 1, hexafluoro-2,2-bis (3-
A polyamide (A5) was synthesized using 1 mol of 3,3′-diamino-4,4′-dihydroxyphenyl ether instead of 1 mol of amino-4-hydroxyphenyl) propane, and otherwise the same as in Example 1. Trial manufacture and evaluation were performed. << Example 10 >> The organosilicon compound (S
The amount of 1) added was 6 parts by weight, and the organosilicon compound (S2) was 3 parts by weight for trial production and evaluation.

Comparative Example 1 A trial production and evaluation were carried out in Example 1 without adding a phenol compound. << Comparative Example 2 >> In Example 6, trial production and evaluation were carried out without adding a phenol compound. << Comparative Example 3 >> In Example 7, trial production and evaluation were carried out without adding a phenol compound. << Comparative Example 4 >> The phenol compound (P
1) was not added and 40 parts by weight of the phenol compound (P2) was added for trial production and evaluation. << Comparative Example 5 >> Trial production and evaluation were performed without adding the phenol compound (P2) in an amount of 60 parts by weight of the phenol compound in Example 1.

Comparative Example 6 The procedure of Example 1 was repeated without adding any organosilicon compound. << Comparative Example 7 >> 8 parts by weight of the organosilicon compound (S1) obtained by reacting γ-aminopropyltriethoxysilane with maleic anhydride, γ-aminopropyltriethoxysilane and 3,3 ′, 4 , 4′-Benzophenonetetracarboxylic acid dianhydride (S3) was reacted in the same manner as in Example 1 except that the addition amount of the organosilicon compound obtained was increased to 4 parts by weight. << Comparative Example 8 >> Phenol compound (P
0.5 parts by weight of 1) and 0.2 parts by weight of the phenol compound (P2) were added for trial production and evaluation. << Comparative Example 9 >> Phenol compound (P
5 parts by weight of 2) was added in place of the phenol compound (P5), and 10 parts by weight of the phenol compound (P1) was used as it was for trial production and evaluation. << Comparative Example 10 >> Phenol compound (P
10 parts by weight of 1) was added in place of the phenol compound (P6), and 5 parts by weight of the phenol compound (P2) was used as it was for trial production and evaluation. The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 10 are shown in Tables 1 and 2.

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

[0070]

[Chemical 28]

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

According to the present invention, it is possible to obtain a positive type photosensitive resin composition which is capable of obtaining a pattern having a high sensitivity and a high residual film ratio and being excellent in adhesiveness between a sealing resin and a substrate.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-5-197153 (JP, A) JP-A-7-128846 (JP, A) JP-A-6-95368 (JP, A) JP-A-9- 302221 (JP, A) JP 9-146274 (JP, A) JP 9-222729 (JP, A) JP 5-72728 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) G03F ^7/ 00-7/18

Claims (9)

(57) [Claims] 1. 100 parts by weight of polyamide (A) represented by general formula (1) and photosensitive diazoquinone compound (B)
1 to 100 parts by weight and a total of 1 to 30 parts by weight of the phenol compounds (C) of the general formulas (2) and (3) and the general formula (4),
A positive photosensitive resin composition comprising 1 to 10 parts by weight of at least one organic silicon compound (D) selected from (5) and (6). [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] 2. X in the polyamide of the general formula (1)
The positive-type photosensitive resin composition according to claim 1, which is selected from the following. [Chemical 7] 3. Y in the polyamide of general formula (1)
Is a positive photosensitive resin composition according to claim 1 or 2, selected from the following. [Chemical 8] 4. The positive photosensitive resin composition according to claim 1, 2 or 3, wherein the photosensitive diazoquinone compound (B) is selected from the following. [Chemical 9] 5. The positive photosensitive resin composition according to claim 1, wherein the phenol compound of the general formula (2) has the following structure. [Chemical 10] 6. The positive photosensitive resin composition according to claim 1, wherein the phenol compound of the general formula (3) has the following structure. [Chemical 11] 7. The positive photosensitive resin according to claim 1, wherein the silicon compound represented by the general formula (4) is a reaction product of γ-aminopropyltriethoxysilane and maleic anhydride. Composition. 8. The silicon compound of the general formula (5) is a reaction product of γ-aminopropyltriethoxysilane and 4,4′-oxydiphthalic anhydride. Positive photosensitive resin composition of. 9. The silicon compound represented by the general formula (6) comprises γ-glycidoxypropyltrimethoxysilane, 3,3 ′,
The positive photosensitive resin composition according to claim 1, which is a reaction product with 4,4′-benzophenone tetracarboxylic acid dianhydride.