JPH02226150A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To improve heat resistance by dispersing a specific photosensitive agent and sensitizer into specific polyamic acid thereby generating the crosslinking with a small quantity of irradiation to provide a high sensitivity and further fully thermally splashing the photoset acrylates of the polyimide after thermal curing. CONSTITUTION:The compsn. contains the polyamic acid formed by copolymerizing 5 to 50wt.% silicone diamine expressed by formula I (where n is 3 to 50) and the amine compd. expressed by formula II (where Rf is -H, CH3, C2H5; R2 is H, CH3; X is O or NH; n is 2 to 3) as the photosensitive agent. Further, the compsn. contains the biscumarine compd. which is expressed by formula III (where R1, R2 are H, alkoxy group, dialkyl amino group) and is subjected to carbonyl substitution at the 3-position as the sensitizer. The compsn. is formed by using 20 to 200pts.wt. photosensitive agent and 1 to 20pts. wt. sensitizer per 100pts.wt. polyamic acid as the essential components. The photosetting property of the high sensitivity is obtd. in this way and further, the film after thermosetting is highly resistant to heat, heat cycle, heat shock and moisture.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a highly heat-resistant photosensitive resin composition having a small elastic modulus and low water absorption.

[Conventional technology] Conventionally, surface protection films of semiconductor elements, glabellar insulating films, etc.
Polyimide, which has excellent heat resistance, excellent electrical insulation properties, and AWI strength, is used2-3), but in recent years, there has been an increase in the size of semiconductor devices and the thinner and smaller size of encapsulating resin packages. Heat cycle resistance due to transition,
There is a demand for significant improvements in heat shock resistance, etc., and it has become difficult to meet these demands with conventional polyimide resins.

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, 62223228, etc.).

On the other hand, a technique that imparts photosensitivity to polyimide itself in order to simplify the complicated process of creating polyimide patterns has recently attracted attention.

For example, a polyimide precursor composition to which a photosensitive group is added with an ester group having a structure as shown in the following formula (IV) (Japanese Patent Publication No. 5530207, No. 55-41422) or polyamic acid dimerized with actinic radiation. Alternatively, compositions 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) are known.

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

Using polyimide with photosensitivity not only produces a light purple effect in the pattern creation process, but also eliminates the need to use highly toxic etching solutions, making it safer and more environmentally friendly. It is expected that this layer will become an important 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 that although silicone groups are introduced into polyamic acid to lower the elastic modulus, it has high sensitivity 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 cycleability, heat shock resistance, moisture resistance, etc.

[Means to solve the problem]

The present invention uses (A) a polyamic acid containing 5 to 50% by weight of a silicone diamine represented by the following general formula (1) (in which n is 3 to 50) and (B) a photosensitizer having the following general formula: Formula (■) (in the formula, R, is -
H, CH2, Cz Hs, Rz is HlCH, X is O
or NH, where n is 2 to 3) and (C) as a sensitizer, the following general formula (]I[)C in the formula R,
, R, is H1 alkoxy group, dialkylamino group), and a Vistamarin compound substituted with carbonyl at the 3-position is added to 100 parts by weight of polyamic acid, 20 to 200 parts by weight of a photosensitizer, and sensitized. This is a photosensitive resin composition containing 1 to 20 parts by weight of a photosensitive agent as an essential component.

[For production]

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

n in the silicone diamine is 3 to 50.

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

Furthermore, if a long-chain silicone diamine with n exceeding 50 is used, the reaction with tetracarboxylic dianhydride will be difficult to proceed quantitatively, and it will remain as an unreacted product, resulting in a large molecular weight (not only a large molecular weight but also a high flexibility). This is not preferable because it lowers the temperature 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-phenylene-diamine, l-isopropyl-2,4
-phenylene-diamine, p-phenylene-diamine,
4,41-diamino-diphenylpropane, 3,3'-
Diamino-diphenylpropane, 4,4'-diamino-
Diphenylethane, 3,3°-diamino-diphenylethane, 4,41-diamino-diphenylmethane, 3.3
°-Diamino-diphenylmethane, 4.4′-diamino-diphenyl sulfide, 3,3°-diamino-diphenyl sulfide, 4.4”-diamino-diphenyl sulfone, 3.3°-diamino-diphenyl sulfone, 4,
4°-diaminodiphenyl ether JLt, 3,3°-
Diamino-diphenyl ether, benzidine, 313'-diamino-biphenyl, 3,3'-dimethyl-4,4
'-Diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4,4'-diamino-p-terphenyl, 3
, 3”-diamino-p-terphenyl, bis(p-amino-cyclohexyl)methane, bis(p-β-amino-
t-Butylphenyl) ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1
-dimethyl-5-amino-pentyl)benzene, 1.5
-diaminonaphthalene, 2,6-diaminonaphthalene,
2.4-bis(β-amino-t-butyl)toluene, 2
．． 4-diamino-toluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2.6-
Diamitoupyridine, 2,5-diamino-pyridine, 2
．． 5diamino-13,4-oxadiazole, 1,4-
Diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine,
2.2-dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2.5-dimethyl-hexamethylene-diamine, 3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2.5-dimethyl-hebutamethylene-diamine, 3-methyl-hebutamethylene-
Diamine, 4,4-dimethyl-hebutamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino- Examples include, but are not limited to, 1,10-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino-octadecane, 2,12-diamino-octadecane, 2,17-diamino-icosane, etc. It's not something you can do.

The tetracarboxylic dianhydride component to be reacted with the diamine component may be one type or a mixture of two or more types, but examples of the tetracarboxylic dianhydride used include pyromellitic dianhydride, benzene, 1.2 ,3.4-
Tetracarboxylic dianhydride, 3.3°, 4.4'-benzophenonetetracarboxylic dianhydride, 2.2°, 3.
3'-benzophenonetetracarboxylic 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-L4,5.8-tetracarboxylic dianhydride, Naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4 .8-dimethyl-1,2,
3,5,6,7-hexahytronaphthalene-1.2.5
．． 6-tetracarboxylic dianhydride, 4,8-dimethyl-
1,2,3,5,6,7-hexahytronaphthalene-2
．． 3.6.7-Tetracarboxylic dianhydride, 2.6-cyclonaphthalene-1.4,5.8-tetracarboxylic dianhydride, 2.7-cyclopentane-L, 4.5.8 −
Tetracarboxylic dianhydride, 2.3,6.7-tetrachloronaphthalene-L4.5.8-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 dianhydride, 3.3", 4.4"-p-terphenyltetracarboxylic dianhydride Acid dianhydride, 2.2', 3.3"-p-terphenyltetracarboxylic dianhydride, 2°3.3", 4"
-p-terphenyltetracarboxylic dianhydride, 2.2
-bis(2,3-dicarboxyphenyl)-propanihydride, 2.2-bis(3,4-dicarboxyphenyl)-propanihydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis (3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methanidianhydride, bis(3,4-dicarboxyphenyl)methanidianhydride, bis(2,3-dicarboxyphenyl)methanidianhydride, phenyl)sulfone dianhydride, bis(3,4
-dicarboxyphenyl)sulfone dianhydride, 1.1-
Bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bisq3,4-dicarboxyphenyl)ethane dianhydride, perinine-2,3゜8.9-tetracarboxylic dianhydride, perinine- 3,4,9゜10-tetracarboxylic dianhydride, perinine-4,5゜10,11-tetracarboxylic dianhydride, perinine-5゜6.11.1
2-tetracarboxylic dianhydride, phenanth, syn-1
,2,F,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane -1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, Thiophene-2,3,4,5-
Examples include, but are not limited to, tetracarboxylic dianhydride.

The photosensitive agent (B) in the present invention is an amine compound having an amino group and an acrylic or methacrylic group in one molecule. Representative compounds of this type include N,N-dimethylaminoethyl methacrylate, N,N
-dimethylaminoethyl acrylate, N.

N-diethylaminoethyl methacrylate, N.

N-diethylaminoethyl acrylate, N,N-dimethylaminopropylacrylamide, N.

Examples include, but are not limited to, N-dimethylaminopropylacrylamide.

The blending ratio of the amine compound (B) is that of the polyamic acid (A
) It is desirable to use 20 parts by weight or more and 200 parts by weight or less per 100 parts by weight.

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

If the amount is 200 parts by weight or more, the amount added is so large that even if effective photocrosslinking is performed, scattering shrinkage will be large during heat treatment and cranking will easily occur, which is not preferable.

The sensitizer as component (C) in the present invention is a vistamarin compound substituted with carbonyl at the 3-position, represented by (wherein R+ and Rz are -H5 alkoxy groups and dialkylamino groups). Exacerbating agents for photosensitive resin compositions include benzophenone, acetophenone, anthrone, p
, p-tetramethyldiaminobenzophenone (Michler's ketone), phenanthrene, 2-nitrofluorene,
5-nitroacenaphthene, benzoquinone, N-acetyl-p-nitroanili, 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, but which of these is the vistamarin compound discovered in the present invention? showed superior sensitization effect. The reason for this surprising effect is not yet clear.

Examples of vistamarin compounds include 3,3°-carbonylrubis(7-dinithylaminocoumarin), 3.3'
-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.

The present invention will be explained in detail with reference to Examples below.

〔Example〕

Example 1 Silicone diamine and disiloxane bond are 15(n-
35g (35% by weight in polyamic acid) of 15) and 3°3'
, 45 g of 4.4°-benzophenone tetracarboxylic dianhydride and 20 g of 4.4°-diaminodiphenyl ether
were reacted in an NMP solvent to obtain a polyamic acid solution. 6 parts of N,N-dimethylaminoethyl methacrylate was added to this polyamic acid solution (100 parts by weight in terms of solid content).
0g (60 parts by weight) and 4g (4 parts by weight) of 3,3'-carbonyl-bis(7-dinithylaminocoumarin).
was added and stirred for 3 hours at room temperature to dissolve and react.

The obtained solution was applied onto an aluminum plate using a spinner and dried at 80° C. for one hour using a drier. This film has a Kodak Photographic Step Tablet N12.2.
1 step (In this gray scale, as the number of steps increases, the amount of transmitted light decreases to 1/f2 of the previous step, so the larger the remaining step of the film after development, the higher the sensitivity.) When the pattern was irradiated with , developed using a developer containing 60% by weight of N-methylpyrrolidone and 40% by weight of methanol, and further rinsed with isopropyl alcohol, the pattern remained up to 14 steps, indicating high sensitivity.

Separately, the entire surface was exposed, developed, and rinsed, and the film was then heat-cured for 30 minutes each at 150.250.350"C. The tensile modulus (JIS K-6760) of this polyimide film was 110 kg/Wm”
, thermal decomposition starting temperature is 420°C1 water absorption rate (J Is
K-6911) was 0.8%.

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

Example 2.3 The same procedure as in Example 1 was carried out, except that the number of siloxane bonds in the silicone diamine was changed to 5 and 40. 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 photosensitive acrylate added, and the amount of sensitizer added, and the results shown in Table 1 were obtained.

In Comparative Example 1, the amount of silicone diamine added was as small as 4% by weight, so the tensile modulus was too high.

In Comparative Example 2, the amount of silicone diamine added was 70% 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 2, and cracks occurred during film formation due to lack of flexibility.

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

In Comparative Example 5, since the amount of photosensitive acrylate added was as small as 15 parts by weight, sufficient crosslinking was not achieved upon exposure, resulting in low sensitivity.

In Comparative Example 6, since the amount of photosensitive acrylate added was too large (250 parts by weight), scattering shrinkage during high temperature curing was large and cracks were generated.

In Comparative Example 7, since the photosensitive acrylate had an amino group, it was not compatible with polyamic acid and a uniform film could not be formed.

In Comparative Example 8, since the amount of sensitizer added was as small as 0.3 parts by weight, a sufficient photoinitiation reaction could not be obtained and the sensitivity was low.

In Comparative Example 9, the amount of sensitizer added was too large (25 parts by weight), so the sensitizer precipitated during drying and a uniform film could not be obtained.

Comparative Example 10 used a sensitizer other than the biscoumarin compound, so the sensitivity was low and it was not practical.

〔Effect of the invention〕

5 to 5 silicone diamines are added to obtain the effect of low elastic modulus.
Polyamic acid containing 50% by weight of metal 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, since the photosensitizer and the sensitizer are uniformly dispersed in the polyamic acid, crosslinking occurs with an extremely small amount of light irradiation, resulting in high sensitivity.

Furthermore, the heat-cured polyimide has excellent heat resistance because all of the photo-cured acrylates are dispersed by heat, and since it is silicone-modified, it has a low elastic modulus and low water absorption, which are extremely excellent effects.

Procedural amendment 1990 March

Claims (1)

[Claims] (1) (A) Polyamic acid containing 5 to 50% by weight of silicone diamine represented by the following formula (I) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼…………(I) (In the formula, n is 3 ~50) (B) Amine compound represented by the following formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼…………(II) (In the formula, R_1 is -H, -CH_3, -C_2H_5, R
_2 is -H, -CH_3, X is -O-, -NH-, n is 2 to 3) (C) Biscoumarin compound substituted with carbonyl at the 3-position represented by the following formula (III) ▲ Numerical formula, chemical formula, There are tables, etc. ▼…………(III) (In the formula, R_1 and R_2 are -H, alkoxy group, dialkylamino group) to 100 parts by weight of (A), 20 to 200 parts by weight of (B), ( C) A photosensitive resin composition comprising 1 to 20 parts by weight.