JPH0391752A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin composition having highly sensitive photogardenability and freed of cracking at the time of development by incorporating di- or tri-functional aminoacrylate structure in the monomer units of a polyamic acid and a photosensitizer in the polyamic acid. CONSTITUTION:The photosensitive resin composition high in reliability contains as the essential components, (A): the polyamic acid represented by formula I, (B): the polyfunctional aminoacrylate having 2 or 3 units of (meth) acrylic acid groups in one molecule, represented by formula II, and (C): the photosensitizer having an absorption maximum wavelength in 330-500 nm. It is preferred that the polyamic acid is converted into an aromatic polyimide after heat hardening in order to enhance heat resistance of the polyimide film. The use of the monofunctional aminoacrylate having only one (meth) acrylic acid group permits cross-linking structure not to be obtained by light irradiation, accordingly, sensitivity to be lowered, and cracking of a pattern to be made liable to occur.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive resin composition that has excellent optical properties such as sensitivity and development properties, and is highly heat resistant.

[Technology from 1κ] Conventionally, surface protection films of semiconductor elements, glabella insulating films, etc.
Polyimide is used because it has excellent heat resistance, as well as excellent electrical insulation and mechanical strength, but recently technology has been developed to impart photosensitivity to polyimide itself in order to simplify the complicated process of creating polyimide patterns. It is attracting attention. For example, a polyimide precursor introduction product (Japanese Patent Publication No. 30207/1983) in which a photosensitive group is added with an ester group having a structure as shown in the following formula, or a polyamic acid that is converted into 2ffi or a polymerizable carbon monomer with actinic radiation. A composition containing a compound containing a carbon double bond and an amino group or a quaternized salt thereof (
For example, Japanese Unexamined Patent Publication No. 145794/1984) is known.

Are any of these appropriate? Dissolved in agent A, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed, and rinsed to obtain the desired pattern.
Further heat treatment is required. It has a polyimide coating.

Using polyimide with photosensitization not only simplifies the pattern creation process, but also eliminates the need to use highly toxic etching solutions, making it safer and less polluting. It is expected that this technology will become an important technology in the future. However, when such conventional photosensitization technology is applied to polyimide precursor compositions with photosensitive groups provided with ester groups,
Because the photosensitive group is difficult to scatter during heat curing, only films with low heat resistance after curing can be obtained, making it difficult to use in the semiconductor industry. Compositions containing possible carbon-carbon double bonds and amino groups, or their quaternized salts, have extremely low sensitivity even when exposed to ultraviolet rays, and may also cause cracks or film deformation during development. It was not sufficient to process it in the manufacturing process normally used in the semiconductor industry because of the tendency for this to occur. [Problems to be Solved by the Invention] The object of the present invention is to have high sensitivity photocurability by blending a bi- or trifunctional amino acrylate and a photosensitizer into a polyamic acid. Another object of the present invention is to provide a photosensitive resin composition that does not cause any cracks during development, has little film loss, and has a cured film that has excellent heat resistance, heat cycle resistance, heat shock resistance, moisture resistance, etc. .

[! ! Means to solve problem w]

(1) (A) Acrylic or methacrylic acid in one molecule of polyamic acid (B) represented by the following formula [I] (wherein R1 and R2 are aromatic cyclic groups, and m is an integer of 1 or more). The following formula (II) X having 2 to 3 groups (wherein, X is -H or -CH3 group, Y is -CHa+-C
2 H=s. -C B H 7 or -ph group, Z is -
C zH4-, -C aHe-, -Cl 2CHOH
CH2- group, 0 is an integer of 2 to 3, p is an integer of O to 1, and the maximum absorption wavelength (input max) of polyfunctional aminoacrylate (C) represented by 0+p=3 is 330 to 500
By using a sensitizer of nm as an essential component, it becomes possible to obtain a highly reliable photosensitive resin composition. [Function] Polyamic\I! in the present invention! It is desirable that i(A) becomes an aromatic polyimide after heat curing in order to improve the heat resistance of the polyimide coating. Such polyamic fif (A) is usually obtained by reaction of an aromatic diamine and an aromatic tetracarboxylic dianhydride.

As the aromatic diamine used to synthesize polyamic acid, the following diamines are used.

For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylbroban, 4.49
-diaminodiphenylmethane, benzidine, 4,4'-
Diaminodiphenyl sulfide, 4,4'-diaminophenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3.3'
-diaminodiphenyl ether, 4.4”-diaminop-terphenyl, 2,6-diaminopyridine, bis(4-aminophenyl)phosphine oxide, bis(4-diaminophenyl)phosphine oxide, bis(4-diaminophenyl)phosphine oxide,
-aminophenyl)-1N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine,
2,4-bis(β-amino-t-butyl)-1-luene, bis(p-β-amino-t-butylphenyl)ether, p-bis(2-methyl-4-aminobentyl)
These include benzene, p-bis(1,1-dimethel-5-aminobentyl)benzene, 2,4-diaminotoluene, m-xylylenediamine, p-xylylenediamine, and the like. As the diamine component used in the present invention, in addition to the above-mentioned aromatic diamines, silicone diamines and aliphatic diamines can also be used in combination to impart various properties.

In addition, the aromatic tetracarboxylic dianhydride component used in polyamic acid synthesis may be one type or a mixture of two or more types, but the aromatic tetracarboxylic dianhydride used is biromellitic dianhydride. thing, 3.3',
4.4'-benzophenonetetracarboxylic dianhydride, 2,3,6.7-naphthalente-1-lacarboxylic dianhydride, 3,3'',4,4ξ diphenylde-1-lacarboxylic dianhydride, 2. 2', 3.3'-diphenyltetracarboxylic dianhydride, 2,3.3',4'-diphenyltetracarboxylic dianhydride, 3,3''. 4.4” p-terphenyltetracarboxylic dianhydride, 1,2,5,f
3,-naphthalenetetracarboxylic dianhydride, 2,2-
Bis(3,4-dicarboxydiphenyl)ether dianhydride, naphthalene-1,2,4. 5-tetracarboxylic dianhydride, naphthalene-1,4,5,8,-tetracarboxylic dianhydride, 4,8-dimethyl-1,2.3,
5,6,7,-hexahydro-naphthalene-1.2,5.
6-Tetracarboxylic dianhydride, 2,6,-dichloronaphthalene, -1.4,5.8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1.4,5.8-tetra Carboxylic dianhydride, phenanthrene-1,2,9
．． 10-Tetracarboxylic dianhydride, pyrrolidine-2.
3,4,5,-tetracarboxylic dianhydride, virazine-
2.3,5,f3,-tetracarboxylic dianhydride, 2,
2-bis(2,5-dicarboxyphenyl)propanihydride, 1.1-bis(2,3-dicarboxyphenyl)ethanihydride, 1.1-bis(3,4-dicarboxyphenyl)ethanihydride bis(2,3-dicarboxyphenyl)methanihydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1.2
, 3,4-butanetetracarboxylic dianhydride, and thiophene-2.3,4.5-tetracarboxylic dianhydride. In addition to the above-mentioned aromatic tetracarboxylic dianhydrides, silicone-based tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides can of course be used in combination to give examples of small characteristics.

The polyfunctional aminoacrylate (B) in the present invention is a tertiary aminoacrylic compound having two or three acrylic or methacryl groups in one molecule. Monofunctional aminoacrylates with one acrylic or methacrylic group in one molecule cannot form a crosslinked structure even when irradiated with light.
It is undesirable because the sensitivity is low, and cracks occur in the pattern during development, resulting in a large amount of film loss. Furthermore, tertiary aminoacrylic compounds having four or more acrylic or methacrylic groups in one molecule are complicated to synthesize and are difficult to use industrially.

Examples of the polyfunctional aminoacrylate (B) include N-methyldiethanolamine dimethacrylate I, N-ethyldiethanolamine dimethacrylate, N-methyldiethanolamine diacrylate, N-ethyldiethanolamine diacrylate, and N-n-probyldiethanolamine diacrylate. Methacrylate, N-11-probyldiethanolamine diacrylate, N-methyldibrobanol dimethacrylate, N-ethyldibrobanol dimethacrylate, triethanolamine trimethacrylate,
Examples include, but are not limited to, triethanolamine triacrylate. Furthermore, as the aminoacrylate component used in the present invention, in addition to the polyfunctional aminoacrylates mentioned above, monofunctional aminoacrylates and polyfunctional acrylates without amino groups can of course be used in combination to impart various properties. Further, the sensitizer (C) in the present invention has a range of 330 to 500 nn+
It is a compound with maximum absorption wavelength (λmax) at . λ
If max is 330 nm or less, light is absorbed by the polyamic acid itself and no photoreaction is possible, which is not preferable. Moreover, if it is 500 nm or more, it is not preferable because it will undergo a photoreaction with visible light, making it necessary to use a shielded room in the working area, and the ease of handling will deteriorate. Sensitizers of the present invention include, but are not limited to, Example 5 C104 CIO'''4.

〔Example〕

Example l 3.3'4.4'-benzophenone tetracarboxylic dianhydride 290 g (0.9 mol), 4,4''-diaminodiphenyl ether 200 g (1.0 mof) ftN-
A polyamic acid solution was obtained by reaction in methylpyrrolidone. The obtained polyamic acid solution}l! (Solid content of boriamic acid) 80 ffiffi parts of N-methyldiethanolamine dimethacrylate cut into 100 parts by weight and 5 parts by weight of Michler's ketone were stirred at room temperature for 3 hours to dissolve and react.

The obtained solution was applied onto an aluminum plate using a swinner and dried at 80° C. for one hour using a drier to obtain a film.

This film was coated with Kodak Photographic Step Tablet No. 2, 21 steps (In the above gray scale, each time the number of steps increases, the amount of transmitted light decreases to 170 of the previous step, so the larger the number of steps remaining in the film after development, the higher the sensitivity.) When the pattern was stripped and then developed using a developer containing 60 parts by weight of N-methylpyrrolidone and 40 parts by weight of methanol, and further rinsed with isobrobyl alcohol, it was found that the pattern remained up to 12 steps, indicating high sensitivity.

Next, when exposure and development were carried out in the same manner as in the patterning experiment described above using a resolution measurement mask manufactured by Toppan Printing (Toppan Test Char No. 1), no cracks occurred and almost no decrease in film thickness was observed. Ta. Further, the entire surface was exposed, developed, and rinsed separately, and then heated and cured at 150, 250, and 350°C for 30 minutes each. The thermal decomposition initiation temperature of this polyimide film is 410°C
Met. The resulting photosensitive resin composition was highly sensitive, did not cause cracks or film loss during development, and had the excellent effects of high heat resistance. The evaluation results are shown in Table 1. Examples 2 and 3 Photosensitive resin compositions were obtained by performing the same operations as in Example 1 except for changing the type of polyfunctional 11-hyaminoacrylate (B) in Example 1 according to Table 1. We conducted an evaluation.

The photosensitive resin compositions obtained in Examples 2 and 3 had high sensitivity, no cracking, and no film loss.
Furthermore, the extremely excellent effect of having heat resistance of 400° C. or higher was also obtained.

The evaluation results are shown in Table 1.

Comparative Example 1 The polyfunctional amino acrylate (B) component of the example was
A photosensitive resin composition was obtained by carrying out the same operation as in Example 1 except that N-dimethylaminoethyl methacrylate was used.

The resulting photosensitive resin composition had low sensitivity because the aminoacrylate component was monofunctional, and cracks were observed at the corners of the pattern. Furthermore, the amount of film loss increased by more than 1O times compared to Examples 1 to 3, and it was found that the accuracy with the mask was significantly different, indicating that the practicality was low. The evaluation results are shown in Table 1.

Comparative Examples 2 to 5 Polyfunctional aminoacrylate-1-(
A photosensitive resin composition was obtained by carrying out the same operation as in Example 1 by changing the types of component B) and sensitizer (C) component, and was further evaluated in the same manner as in Example 1. The functional amino acrylate (B) component is N-
This is a case in which n-octyldiethanolamine dimethacrylate was used instead. Because the alkyl group is a long chain, its compatibility with polyamic acid decreases, and it completely peels off during development, making it impossible to create a pattern. Comparative Example 3 contains 1 polyfunctional aminoacrylate (B) component,
This is the case where the change was made to 6-hexanediol dimethacrylate. Since it did not have an amino group, the compatibility with polyamic acid decreased as in Comparative Example 2, and it was completely peeled off during development, making it impossible to create a pattern.

Comparative Example 4 uses 3,3-dimethyl-4-me1-xybenzophenone as the sensitizer (C) component, but since the λIIIax of this sensitizer is 296 nm, it can be used efficiently. It was found that the photo-initiated reaction was not possible and the entire pattern was washed out during development, making it impractical.

Comparative Example 5 uses a tetraphenylborphyline zinc complex as the sensitizer (C) component, but since the WaX of this sensitizer is 650 nm, it undergoes a photoreaction during processing and the pattern cannot be formed by development. I couldn't get it. The evaluation results are shown in Table 1. [Effect of the invention] Photosensitive polyamic acid synthesized by blending an acrylic compound having an amino group is developed and patterned by pseudo-crosslinking due to the interaction between the amino group and the carboxyl group of the polyamic acid using conventional photosensitization technology. Therefore, the sensitivity was low even when irradiated with light, cracks appeared in the pattern during development, and a large amount of film loss occurred, making it unsuitable for the semiconductor industry. However, in the present invention, di- or tri-functional aminoacrylate is added to the aromatic polyamic acid (A).
(B) and absorption maximum wavelength (λmax) is 330 to 50
Since the sensitizer (C) having a particle diameter of 0 nm is blended, as a result, crosslinking occurs with an extremely small amount of light irradiation, resulting in high sensitivity.

In addition, since a crosslinked structure is obtained using only the di- or tri-functional aminoacrylate (B), there is no occurrence of cracks or thinning of the film during development. Furthermore, the heat resistance of the polyimide film after heat curing is due to the fact that the aminoacrylate (B) is simply blended into the aromatic polyamic acid (A), and the acrylate is not introduced into the polyimide skeleton through covalent bonds. At the same time, the very excellent effects of being easily scattered by heating during curing, maintaining the heat resistance inherent to aromatic polyimide, and exhibiting high heat resistance were obtained.

In addition, in the present invention, essential components (A), (B), (
There was no problem when additives other than C) were added to impart various properties.

Claims (1)

[Claims] (1) (A) The following formula [ I ] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [ I ] (In the formula, R_1 and R_2 are aromatic cyclic groups, m is an integer of 1 or more) Polyamic acid ( B) The following formula [II] has 2 to 3 acrylic or methacrylic groups in one molecule ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, X is -H or -CH_3 group, Y is -CH_3 ,−
C_2H_5, -C_3H_7 or -Ph group, Z is -C
_2H_4-, -C_3H_6-, -CH_2CHOH
CH_2- group, o is an integer of 2 to 3, p is an integer of 0 to 1, (C) absorption maximum wavelength (λmax) is 330 to 50
A photosensitive resin composition containing a 0 nm sensitizer as an essential component.