JPH02144539A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosetting property of high sensitivity even if a silicone group is introduced into polyimide acid to lower the modulus of elasticity by uniformly dispersing a specific multifunctional acrylate and sensitizer into the polyamide acid synthesized by incorporation of a silicone diamine therein. CONSTITUTION:This compsn. contains the polyamide acid contg. 5 to 50wt.% silicone diamine expressed by formula I, the multifunctional acrylate having >=2 acryl groups in one molecule and having <=500mol.wt., and the sensitizer. The sensitizer is a biscumarine compd. carbonyl-substd. in the 3rd position expressed by formula II. The multifunctional acrylate is dispersed at 20 to 200pts.wt. and the sensitizer at 1 to 20pts.wt. into 100pts.wt. polyamide acid. In formulas I, II, n denotes 3 to 50; R1, R2 denote a hydrogen atom, alkoxy group, dialkylamino group. The excellent effects of the high sensitivity plus the low modulus of elasticity, high heat resistance and low water absorption are simultaneously obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly heat-resistant photosensitive resin composition that has a low elastic modulus and low water absorption.

[Conventional technology]

Conventionally, surface protection films, interlayer insulation films, etc. of semiconductor devices are
Polyimide is used because it has excellent heat resistance, as well as outstanding electrical insulation and mechanical strength. However, in recent years, semiconductor devices have become larger, sealing resin bars and cages have become thinner and smaller, and
Due to this transition, there are significant demands for improved heat cycle resistance, heat shock resistance, etc., and it has become difficult for conventional polyimide resins to meet these demands.

As a countermeasure against this problem, it is known that, for example, a silicone component is introduced into polyimide resin to lower the elastic modulus. (JP-A-61-64730, No. 62-223228, etc.) On the other hand, in order to simplify the complicated process of creating polyimide patterns, a technology that imparts photosensitivity to polyimide itself has recently attracted attention. There is.

For example, polyimide precursor compositions provided with photosensitive groups using ester groups having the structure shown in the following formula (Japanese Patent Publication Nos. 55-30207 and 55-41422) or polyamic acids dimerized with actinic radiation or , a composition containing a compound containing a polymerizable carbon-carbon double bond and an amino group or a quaternized salt thereof (for example, JP-A-54-145794) is known.

All of these are dissolved in an appropriate organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and further heat-treated to form a polyimide. It is a coating.

Using polyimide with photosensitivity not only simplifies pattern creation, but also eliminates the need for highly toxic etching solutions, making it safer and less polluting. Photosensitizing polyimide It is expected that this technology will become an important layer technology in the future as the elastic modulus of polyimide becomes lower. .

However, when such conventional photosensitization technology is applied to polyimide with a low elastic modulus in which silicone groups are introduced into the polyimide component, it is difficult to pattern the polyimide even when irradiated with ultraviolet rays, or the sensitivity is extremely low. The exposure equipment used was insufficient for processing.

[Problem to be solved by the invention]

The purpose of the present invention is to reduce the elastic modulus by introducing silicone groups into polyimide acid.
It has highly sensitive photocurability, and the film after curing is heat resistant.
It is an object of the present invention to provide a photosensitive resin composition having excellent heat cycle resistance, heat crack resistance, moisture resistance, etc.

[Means to solve the problem]

The present invention comprises (A) a silicone diamine represented by the following general formula (in the formula, n is an integer of 3 to 50) containing 5 to 50% by weight of hydrous lyamic acid, and (B) hydrated lyamic acid in one molecule. Other functional acrylate-I, which has two or more acrylic or methacrylic groups and has a molecular weight of 500 or less,
(C) As a sensitizer.

A bistamarin compound substituted with carbonyl at the 3-position represented by the following general formula (wherein R+ and Rz represent a hydrogen atom, an alkoxy group, a dialkylamino group, etc.) is added to a polyamic acid 100
This is a photosensitive resin composition containing 20 to 200 parts by weight of a multisensitizing acrylate and 1 to 20 parts by weight of a sensitizer as essential components.

In the present invention, silicone diamine is added to lower the elastic modulus of the polyimide coating and reduce water absorption.

n in silicone diamine is 3-5o.

When n is 3 or less, the effect of lowering the elastic modulus cannot be obtained, which is not preferable.

In addition, if a long-chain silicone diamine with n exceeding 50 is used, the reaction with tetracarboxylic dianhydride will not proceed quantitatively (and will remain in the system as an unreacted product and the molecular weight will not increase). This is not preferable because it reduces flexibility and makes cracks more likely to occur.

The amount of silicone diamine used is preferably 5 to 50% by weight based on the polyamic acid component.

If it is less than 5% by weight, the effect of lowering the elastic modulus cannot be obtained, which is undesirable, and if it exceeds 50% by weight, the heat resistance will be significantly lowered, making it impossible to obtain the characteristics inherent to polyimide resins, which is not preferred.

As the diamine component used in the present invention, in addition to the above-mentioned silicone diamine, the following aromatic diamines can also be used in combination to impart various properties.

For example, m-phenylenediamine, p-phenylenediamine, 4.4'-diaminodiphenylpropane, 4.4
″-diaminodiphenylmethane, benzidine, 4.4′-diaminodiphenyl sulfide, 4.4°-diaminophenyl sulfone, 3,3°-diaminodiphenyl sulfone, 4.4′-diaminodiphenyl ether, 3,
3'-diaminodiphenyl ether, 4.4@diamino-p~rutylphenyl 2,6-diamitupyridine, bis(4-aminophenyl)phosphine oxyto, bis(4
-aminophenyl)-N-methylamine, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2
．． 4-bis(β-amino-1-butyl)-toluene, bis(p-β-amino-L-butylphenyl)ether,
p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,l-dimethyl-5-aminopentyl)
These include benzene, 2,4-diaminotoluene, m-xylylene diamine, p-xylylene diamine, and bis(P-aminocyclohexyl)methane.

Further, the organic tetracarboxylic dianhydride component used in the present invention may be one type or a mixture of two or more types, but examples of the tetracarboxylic dianhydride used include pyromellitic dianhydride, 3.3', 4.4'' Penduphenonetetracarboxylic dianhydride, 2,3°6.7-Naphthalenetetracarboxylic dianhydride, 3.3'.

4.4'-diphenyltetracarboxylic dianhydride, 2.
2°, 3.3'-diphenyltetracarboxylic dianhydride 2.3, 3° 4'-diphenyltetracarboxylic dianhydride, 3.3'', 4.4' -P-terphenyltetracarboxylic acid dianhydride, 1.2,5.6-naphthalenetetracarboxylic dianhydride, 2.2-bis(3,4-dicarboxydiphenyl)propanihydride, 3,4.9.10-
Perylenetetracarboxylic dianhydride, bis(3,4-dicarboxydiphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, naphthalene-1,2,4,5
-Tetracarboxylic dianhydride, naphthalene-1,4,5
, 8-tetracarboxylic dianhydride, 4,8-dimethyl-
1,2,3,5,6゜7-hexahydrocafthalene-1
．． 2.5.6-Tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1.4゜5.8-te)-racarboxylic dianhydride, 2.7-cyclonaphthalene-1.4,5
．． 8-tetracarboxylic dianhydride, 2.3.4.7-titrachloronaphthalene-1.4,5.8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride Anhydride, cyclopentane-1°2.3
゜4-teI-lacarboxylic dianhydride, pyrocillin-2,
3,4,5-tetracarboxylic dianhydride, pyrazine 2゜3.5.6-tetracarboxylic dianhydride, 2,2-bis(2,5dicarboxyphenyl)propanihydride, 1
．． 1-bis(2,3-dicarboxyphenyl)ethanihydride 11.1-bis(3,4-dicarboxyphenyl)
Ethanide dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 1, 2.3.4-butanetetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, and the like.

The polyfunctional acrylate component (B) in the present invention is an acrylic compound having two or more acrylic or methacrylic groups in one molecule and having a molecular weight of 500 or less. Monofunctional acrylates, which have one acrylic group in one molecule, cannot be photopatterned because a crosslinked structure cannot be obtained even when irradiated with light, and if the molecular weight is 500 or more, it may be difficult to dissolve them uniformly. Not only is it difficult, but it remains in the polyimide film without heat scattering even during heat curing.
This is not preferable because heat resistance is significantly reduced.

Polyfunctional acrylate-11B) includes ethylene glycol diacrylate, ethylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, and 1.6-hexanediol. Diacrylate, 1.6-
Hexanediol diacrylate, neoveothyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate-1, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, bisphenol A dimethacrylate, etc., but are not limited to these.

Further, the blending amount of the polyfunctional acrylate is preferably 20 to 200 parts by weight based on 100 parts by weight of the solid content of the polyamic acid.

If it is less than 20 parts by weight, a sufficient photocrosslinked product will not be obtained and will all dissolve during the phenomenon, which is not preferable.

If the amount is 200 parts by weight or more, the addition amount is so large that even if effective photocrosslinking is performed, scattering shrinkage is large and cracks are likely to occur during heat treatment, which is not preferable.

The sensitizer as component (C) in the present invention is a biscoumarin compound substituted with carbonyl at the 3-position, represented by (wherein R, R1 is a hydrogen atom, an alkoxy group, or a dialkylamino group). Sensitizers for photosensitive resin compositions include benzophenone, acetophenone, anthrone, p,p'-tetramethyldiaminobenzophenone (Michler's ketone), phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-
Acetyl p-nitroaryne, p-nitroaniline, 2
-ethylanthraquinone, 2-tert-butylanthraquinone, N-acetyl-4-nitro-1-naphthylamine, biclamide, 1,2-benzanthraquinone,
3-methyl-1,3-diaza-1,9-benzanthrone, P+ p'-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, benzyl, 1.2-naphthoquinone, etc. are used. However, the biscoumarin compound discovered in the present invention showed a sensitizing effect superior to any of these. The reason for this surprising effect is not yet clear.

Examples of biscoumarin compounds include 3.3"-carbonyl, bis(7-diethylaminocoumarin) 3.3"-
Examples include carbonyl, bis(5,7-simethoxycarbonylcoumarin), and the like.

The amount of the sensitizer to be blended is essentially 1 to 20 parts by weight per 100 parts by weight of the solid content of the polyamic acid, and other sensitizers may also be used in combination.

If it is less than 1 part by weight, photocuring will not proceed quickly, which is undesirable. If it is more than 20 parts by weight, crystals will precipitate during film production due to low solubility in polyamic acid. The surface is also eluted, which is not preferable.

[Effect of the invention] In order to obtain the effect of low elastic modulus, 5 to 50% of silicone diamine is added.
Polyamic acid synthesized with a content of 50% by weight has a sea-island structure because it contains a large amount of silicone. For this reason, with conventional photosensitization techniques, the photosensitive group does not dissolve well in the silicone portion, making it impossible to obtain a good pattern.

However, in the present invention, the polyfunctional acrylate and the sensitizer are uniformly dispersed in the polyamic acid, and as a result, crosslinking occurs with an extremely small amount of light irradiation, resulting in high sensitivity.

Furthermore, the photocured acrylate of the polyimide after thermosetting is uniformly dispersed by heat, resulting in excellent heat resistance, and the silicone component provides extremely excellent effects such as low elastic modulus and low water absorption.

Hereinafter, the present invention will be explained in detail with reference to Examples.

(Example) Example 1 A silicone diamine with a siloxane bond of 20 (
p-,! Q) with 30 g (30% by weight in polyamic acid) and 3.3°.

4.4'-benzophenonetetracarboxylic dianhydride 4
5 g and 25 g of 4.4′-diaminodiphenyl ether
were reacted in an NMP solvent to obtain a polyamic acid solution.

This polyamic acid solution (solid content: 10,000 weight, 1
．． 50 g (50 parts by weight) of 4-butanediol dimethacrylate and 3 g (3 parts by weight) of 3,3'-carbonyl, bis(7-diethylaminocoumarin) were added, and the
The mixture was stirred for an hour to dissolve and react.

The obtained solution was applied onto an aluminum plate using a spinner and dried in a dryer at 80°C for one hour. This film uses Kodak Photographic Step Tablet N112.
．． 21 steps (in the above gray scale, each time the number of steps increases, the amount of transmitted light decreases to 17J''2 of the previous step, so the larger the number of steps remaining in the film after development, the higher the sensitivity) and 500 mJ/d ultraviolet light. When the pattern was irradiated with , developed using a developer containing 60% by weight of N-methylpyrrolidone and 40% by weight of methanol, and rinsed with isopropyl alcohol, it was found that the pattern remained up to 12 steps, indicating high sensitivity.

Separately, the entire surface was exposed to light, developed, and rinsed, followed by heat curing at 150, 250, 350, and 400'C for 30 minutes each to produce a film. The tensile modulus (J rsK -6760) of this polyimide film is 120 kg/s
”, thermal decomposition start temperature is 415℃, water absorption rate (JISK-
6911) was 1.0%.

In this way, the extremely excellent effects of high sensitivity, low elastic modulus, high heat resistance, and low water absorption were simultaneously obtained.

Examples 2 and 3 The same procedure as in Example 1 was carried out except that the siloxane bonds of the silicone diamine were changed to 5 and 45. As shown in Table 1, the results showed high sensitivity, low elastic modulus, high heat resistance, and low water absorption.

Comparative Examples 1 to 10 According to the method of Example 1, the amount of silicone diamine added,
The same procedure was carried out by changing the number of siloxane bonds, the type and amount of polyfunctional acrylate added, and the amount of sensitizer added, and the results shown in Table 1 were obtained.

In Comparative Example 1, since the amount of silicone diamine added was as small as 3% by weight, polyamic acid and polyfunctional acrylate were not dissolved and a pattern could not be created.

In Comparative Example 2, the amount of silicone diamine added was 75% by weight.
Because of this increase, it became brittle and its heat resistance also decreased.

In Comparative Example 3, the number of siloxane bonds in the silicone diamine was set to 1, and since the film lacked flexibility, cracking occurred at the time of film formation.

In Comparative Example 4, the number of siloxane bonds in silicone diamine was 1.
20, the reactivity was low and unreacted residual silicone diamine components stood out at the time of film formation, and the sensitivity did not increase.

Comparative Example 5 is a case where a monofunctional acrylate was used, but since it did not become three-dimensional even after exposure, it all washed away during development.

In Comparative Example 6, a high molecular weight acrylate was used, but the sensitivity was not improved due to poor photoreactivity.

In Comparative Example 7, since the amount of polyfunctional acrylate added was as small as 10% by weight, sufficient crosslinking was not achieved and the sensitivity was low.

In Comparative Example 8, the amount of polyfunctional acrylate added was too high (300% by weight), so it was not compatible with polyamic acid and was completely peeled off during development.

In Comparative Example 9, the amount of sensitizer added was as low as 0.3% by weight, so a sufficient photoinitiation reaction could not be obtained and the sensitivity was low.

In Comparative Example 1O, since the amount of sensitizer added was too large (30% by weight), the sensitizer precipitated during drying and a uniform film could not be obtained.

Comparative Examples 11 to 13 The same procedure as in Example 1 was carried out except that the type of sensitizer was changed, and the results shown in Table 1 were obtained.

Some sensitizers did not form a complete pattern, and even if they did, the sensitivity was low.

Claims (1)

[Claims] (1) Polyamic acid (A) containing 5 to 50% by weight of silicone diamine represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, n is 3 to 50), and one molecule Polyfunctional acrylate (B) with a molecular weight of 500 or less, which has two or more acrylic or methacrylic groups in it, and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 hydrogen atoms, alkoxy groups , dialkylamino group) in which the 3-position carbonyl-substituted biscoumarin compound (C) is added to (B) 20 to 100 parts by weight of (A).
A photosensitive resin composition containing 200 parts by weight and 1 to 20 parts by weight of (C) as essential components.