JPH03216657A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosetting property having a high sensitivity by compounding a specific amt. of a specific diacryl amide compd. as an essential component with a copolymer of a silicone diamine and polyamic acid contg. a repeating unit which are respectively specific. CONSTITUTION:The diacryl amide compd. (B) contg. the repeating unit expressed by formula II is compounded as the essential component with the copolymer (A) of 0.5 to 25wt.% silicone diamine expressed by formula I and 99.5 to 75wt.% polyamic acid contg. the repeating unit expressed by formula II at 20 to 300 pts. wt. (B) per 100 pts. wt. (A) and if necessary, a sensitizer and/or initiator is compounded therewith. In the formula I, (n) denotes 1 to 50. In the formula II, R1, R2 denote arm. cyclic group; (n) denotes 1,2; (m) denotes 0 to 2. In the formula III, R3 denotes -H,-CH3, R4, R5 denote -H, -CH3, -CH2OH. The silicone diamine expressed by the formula I has the effect of improving the adhesive property of the polyimide film and lowering the modulus elasticity. Not only the sensitivity is improved but also good pattern free from cracking are obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a highly sensitive and heat-resistant photosensitive polyimide resin composition that has good adhesion, a small elastic modulus, and excellent storage stability. be.

[Conventional technology] Conventionally, surface protection films for semiconductor devices, living room insulation films, etc.
Polyimide resin is used because it has excellent heat resistance and excellent electrical and mechanical properties, but in recent years, 15 conductor elements have become more densely packed and larger, and sealing resin packages have become thinner and smaller. With the shift to surface mounting methods using solder reflow technology, there are demands for significant improvements in 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 the polyimide resin to increase adhesion and lower the elastic modulus. (JP-A-61-64730, JP-A-62-223228, etc.) On the other hand, a technique for imparting photosensitivity to polyimide resin itself has recently attracted attention.

Using polyimide resins that have been given these photosensitizers not only simplifies the pattern creation process compared to polyimide resins that have not been given photosensitivity, but also eliminates the need to use highly toxic etching solutions, making them safer. It is also excellent in terms of pollution, and photosensitization of polyimide resin is expected to become an even more important technology in the future, along with the development of high adhesion and low elastic modulus of polyimide resin.

As the photosensitive polyimide resin, 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 (Japanese Patent Publication No. 55-41422) or as shown in the following formula. A composition in which a compound containing a carbon-carbon double bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation is added to a polyamic acid having the structure (e.g., Japanese Patent Application Laid-open No. 54-145794) etc. are known.

All of these are dissolved in a suitable organic solvent, applied in a face state, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and then heat-treated to form polyimide. It is a coating.

However, when such conventional photosensitization technology is applied to a polyimide resin with high adhesion and low elastic modulus in which a silicone group is introduced into the polyimide resin component, it is difficult to pattern the polyimide resin even when irradiated with ultraviolet rays, or the sensitivity is extremely low. However, the exposure equipment commonly used in the semiconductor industry was insufficient for processing.

Furthermore, when the film thickness of these photosensitive polyimide resins is increased, the photosensitivity is extremely reduced and the proper exposure time is extremely long.

In addition, because of its high water absorption, when the exposed film is stored for a long period of time, it not only takes a long time to develop, but also causes problems such as cracks in the formed pattern.

[Problems to be Solved by the Invention] The purpose of the present invention is to improve adhesion by introducing silicone groups into polyamic acid, and to achieve highly sensitive photocurability despite lowering the elastic modulus. It is an object of the present invention to provide a photosensitive resin composition which has the following properties, has good storage stability, and has an excellent heat resistance after curing.

[Means for Solving the Problems] The present invention provides the following formula (II), which is obtained by copolymerizing 0.5 to 25% by weight of a silicone diamine (rl: 1 to 50) represented by the following formula [1]. A diacrylamide compound (B) represented by the following formula (III) is added to the polyamic acid (A) represented by the following formula (R0, R2: aromatic cyclic group n: 1-2, m: 0-2). III) (In the formula, R 3 : -H , -C H 3R4, R5
: -H, -CH:l, -cH20H) is an essential component, and (B) is 20 to 200 parts by weight per 100 parts by weight of (A).
The purpose is to use a photosensitive resin composition containing parts by weight and, if necessary, a sensitizer and/or an initiator.

[Function] The silicone diamine represented by the general formula CI) used in the present invention has the effect of improving the adhesion of the polyimide film and lowering the elastic modulus.

The degree of polymerization n of the silicone diamine needs to be 1 to 50, and if n is less than 1, the adhesion will be poor. improve,
If the effect of lowering the elastic modulus is not obtained and a long chain silicone diamine with n exceeding 50 is used, the reaction with the tetracarboxylic dianhydride will be difficult to proceed quantitatively, and it will remain as an unreacted product. This is not preferable because it not only does not increase the molecular weight but also reduces flexibility and makes cracks more likely to occur.

The silicone diamine is preferably used in an amount of 0.5 to 25% by weight based on the polyamic acid component.

If it is less than 0.5% by weight, the effects of improving adhesion and lowering the elastic modulus cannot be obtained, and if it exceeds 25% by weight, the heat resistance will be severely reduced, making it impossible to obtain the characteristics inherent to polyimide resins, which is not preferable.

The polyamic acid (A) represented by the general formula [1■] used in the present invention is an acid having an aromatic cyclic group of R■,
It is synthesized using an amine having an aromatic cyclic group as R2. As the acid having an aromatic cyclic group of R0, tricarboxylic acid anhydride with n=1 or tetracarboxylic dianhydride with n=2 are used, and the acid anhydride component may be one type or a mixture of two or more types. But it doesn't matter. The types of acid anhydrides used include, for example, trimellitic anhydride, pyromellitic dianhydride, benzene-1.2,3.4-tetracarboxylic dianhydride, 3.3', 4.4 '-benzophenonetetracarboxylic dianhydride, 2.2', 3.3'
-benzophenone tetracarboxylic dianhydride, 2,3.
3',4'-benzophenonetetracarboxylic 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-hexahydro-naphthalene-1.2,5
．． 6-tetracarboxylic dianhydride, 4,8-dimethyl-
1.2,3,5,6.7-Hexahydride naphthalene-2
．． 3,6.7-Tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1.4,5.8-tetracarboxylic dianhydride, 2.7-dichloronaphthalene-1.4,5.
8-tetracarboxylic dianhydride, 2,3,6,7-tetracarboxylic naphthalene-1,4,5,8-tetracarboxylic dianhydride, l,4,5,8-tetracarboxylic naphthalene- 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-terphenyltetracarboxylic dianhydride, 2
, 3,3″,4″-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propanihydride, 2,2-bis(3,4-dicarboxylic dianhydride) carboxyphenyl) monopropanihydride, bis(2,3
-dicarpoxyphenyl)ether dianhydride, bis(3
．． 4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methanidianhydride, bis(3.4-dicarboxyphenyl)methanidianhydride,
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, berylene-4.5
, 10.11-tetracarboxylic dianhydride, berylene-
5.6,11.12-tetracarboxylic dianhydride, phenanthrene-1,2,7.8-tetracarboxylic dianhydride, phenanthrene-1,2,6.7-tetracarboxylic dianhydride, phenanthrene-1 ,2,9,1O-tetracarboxylic dianhydride, cyclopentane-1.2,3.
4-tetracarboxylic dianhydride, virazine-2.3,5
．． 6-tetracarboxylic dianhydride, pyrrolidine-2,3
, 4.5-tetracarboxylic dianhydride, thiophene-2
．． Examples include, but are not limited to, 3,4.5-tetracarboxylic dianhydride.

As the amine having an aromatic cyclic group for R2, diamine with m = 0, diaminocarboxylic acid with m = 1, diaminodicarboxylic acid with m = 2, etc. are used, and the amine component may be one type or a mixture of two or more types. But it doesn't matter. The types of amines used include, for example, m-phenylene diamine, l-isopropyl-2,4-phenylene diamine,
p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3
'-Diaminodiphenyl ethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide,
3.3'-diaminodiphenylsulfide, 4,4'
-Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, benzidine, 3,3'-diaminodiphenyl, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 3
．． 3′-dimethoxybenzidine, 4.4″-diamino-p-terphenyl, 3.3″-diamino-p-terphenyl, bis(p-amino-hexyl)methane,
Bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-δ~aminopentyl)benzene, ρ-bis(2-methyl-4-aminopentyl)benzene, p-bis(1 .1-dimethyl-5-aminobenthyl)benzene, 1,5-diaminonaphthalene, 2
．． 6-diaminonaphthalene, 2,4-bis(β-amino[monobutyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-
2.5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2.6-diaminopyridine, 2
．． 5-diaminoviridine, 2.5-diamino-1.3
．． 4-Oxadiazole, 1,4-diaminorhexane, biperazine, methylenediamine, ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene -diamine,
2,5-dimethyl-hexamethylene-diamine, 3-methoxyhexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-hexamethylene-diamine, 3-methyl-hexamethylene-diamine, 4,4-
Dimethyl-hebutamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methylnonamethylene-diamine, 2,5-dimethylnonamethylene-diamine, decamethylene-diamine, 1,10-diamino-1. 10-dimethyl-decane, 2,1l-diaminodecane, 1,12-diaminooctadecane,
Examples include 2.12-diamino-octadecane, 2,17-diamino-icosane, diaminosiloxane, 2.6-diamino-4-carboxylic benzene, 3.3'-diamino-4,4'-dicarboxylic benzidine, etc. However, it is not limited to these.

Diacrylamide compound (B) (III) represented by the general formula (III) used in the present invention (wherein R3: -H, -C H3R4, R5:
-H. -CH3. -CH20H) as a photosensitizer has low water absorption, so even if it is applied to a substrate in the buttering process and left for a long time after drying, it will not absorb water easily.
Alternatively, even if the coated film is left exposed for a long period of time and then developed to form a pattern, no cracks will occur in the coated film.

Further, the amount of the diacrylamide compound used is preferably 20 to 200 parts by weight per 100 parts by weight of the polyamic acid component. If it is less than 20 parts by weight, the sensitivity is insufficient;
If it exceeds 0 parts by weight, precipitation will occur and a good film will not be obtained.

Sensitizers used in the present invention include penzophenone, acetophenone, anthrone, p,p'-tetramethyldiaminobenzophenone (Michler's ketone), phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, penzoquinone, N-acetyl-p-nitro Aniline, p-nitroaniline, 2-ethylanthraquinone, 2-tert-butylanthraquinone, N-acetyl-4-nitro-1-naphthylamine, picramide, 1
．． 2-penzanthraquinone, 3-methyl-1,3-diaza 1,9-penzanthrone, p,p'-tetra,
Ethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, l,2-naphthoquinone, 2,5-bis-(4'-diethylaminobenzal)
monocyclopentane, 2,6-bis(4'-diethylaminobenzal)-cyclohexanone, 2,6-bis(4'-diethylaminobenzal)
4'-dimethylaminobenzal)-4-methyl-cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methyl-cyclohexanone, 4,4'-
Bis(dimethylamino)monochalcone, 4.4'-Bis(jethylamino)monochalcone, p-dimethylaminobenzylideneindanone, 1.3-bis(4'-dimethylaminobenzal)monacetone, 1.3- Bis-(4
'-diethylaminobenzal) monoacetone, N-phenyludiethanolamine, N-p-tolyludiethylamine, styryl compounds, coumarin compounds, etc.
They are not limited to these, and can be used alone or in combination.

Initiators used in the present invention include 2,2-dimethoxy-2-phenyl-acetophenone, 1-hydroxy-hexyl-phenyl ketone, 2-methyl-1
4-(methylthio)phenyl]-2-morpholino-1
-Propane, 3.3', 4.4'-tetra(t-butylbaroxycarbonyl)penzophenone, benzyl, penzoin-isoglopylether, penzoin-isobutyl ether, 4.4'-dimethoxybenzyl, 1
．． 4-dibenzoylbenzene, 4-penzoylbiphenyl, 2-penzoylnaphthalene, methyl 10-penzoylbenzoate, 2.2'-bis(O-chlorophenyl)-4,4',5.5'-tetraphenyl-1, 2'
-biimidazole, 10-butyl-2-chloroacridone, ethyl-4-dimethylaminobenzoate, dibenzoylmethane, 2,4-diethylthioxanthone, 3,
3-dimethyl-4-methoxypenzophenone, 2-hydroxy-2-methyl-1-phenylpropan-l-one, l-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1- on, l-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-
1-one, ■-phenyl-1,2-butanedione-2-
(0-methoxycarbonyl)oxime, 1-phenyl-propanebutanedione-2-(O-benzoyl)oxime, 1,2-diphenyl-ethanedione-1-(O-benzoyl)oxime, 1,3-diphenyl- Examples include, but are not limited to, propanetrione-2-(O-benzoyl)oxime, l-phenyl-3-ethoxypropanetrione-2-(0-bezoyl)oxime, glycine compounds, and oxazolone compounds. , can be used alone or in combination.

The heat-resistant, photosensitive resin composition according to the present invention may contain a diluent, a leveling agent, and various other fillers. The photosensitive resin composition according to the present invention is useful not only for use as an IP conductor but also as an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist 1 film, a liquid crystal alignment film, and the like.

The present invention will be specifically explained below using Examples.

Example 1 A mixture of 57 g of 3.3',4.4'-benzophenone tetracarboxylic dianhydride, 33 g of 4.4'-diaminodiphenyl ether as an amine, and 10 g of silicone diamine represented by the following formula was dissolved in N-methylpyrrolidone. The mixture was added and reacted at 20°C for 6 hours.

To the obtained polyamic acid were added 100 g of a diacrylamide compound of the following formula, 4 g of 2-(p-dimethylaminostyryl)penzoxazole, and 8 g of N-phenylglycine, and the mixture was mixed and dissolved at room temperature.

The obtained solution was applied onto an aluminum plate using a spinner and dried at 65° C. for 1 hour using a drier.

Kodak Photographic Step Tablet No. 2 was attached to this film. 21 steps (In this gray scale, each time the number of steps increases, the amount of transmitted light increases by one step from the previous step.)
/f2, so the larger the residual stage after development, the better the sensitivity). After leaving it for 2 days on holiday, it was developed using a developer containing 60% N-methylpyrrolidone and 40% methanol, and then rinsed with isopropyl alcohol. The pattern remained up to 13 steps, with no cracks and high sensitivity. It turned out that.

Next, the coating was applied onto a silicon wafer in the same manner as described above, the entire surface was exposed, development and +7 ounce steps were performed, and then 1
Heat curing was performed at 50, 250, and 350°C for 30 minutes each.

For the adhesion test, 100 pieces were cut into 1 mm square pieces and an attempt was made to peel them off using cellophane tape, but none of them came off, indicating that they had high adhesion.

Separately, it was coated on an aluminum plate, exposed to light over the entire surface, developed, rinsed, and cured with heat, and then the aluminum plate was removed by etching to obtain a film.

Tensile modulus of the obtained film (JIS K-6760
) is small at 140Kg/mm2 (the smaller the better),
The thermal decomposition onset temperature was as high as 430°C (the higher the better).

Comparative Examples 1 to 6 Similar experiments were conducted according to the method of Example 1, changing the number of siloxane bonds and the amount added of the silicone diamine, and the amount of diacrylamide compound as a photosensitizer, respectively.
The results shown in Table 1 were obtained.

In Comparative Example 1, the amount of dimethacrylamide compound added was 1
When the amount was reduced to 0 parts by weight, sensitivity was low and cracks also occurred.

In Comparative Example 2, the crosslinking amount of the dimethacrylamide compound was 2.
When the amount was increased to 10 parts by weight, a clean film could not be obtained.

In Comparative Example 3, the amount of silicone diamine added was 0.2
When it was reduced to % by weight, the elastic modulus could not be lowered.

In Comparative Example 4, when the amount of silicone diamine added was increased to 30% by weight, the film was brittle and the adhesion was poor.

In Comparative Example 5, when the number of siloxane bonds in the silicone diamine was set to n=0, the film lacked flexibility and cracked and fell apart when it was formed into a film.

In Comparative Example 6, when the number of siloxane bonds in the silicone diamine was set to n = 100, the reaction rate was low and unreacted silicone bled onto the film surface and peeled off.

[Effects of the Invention] In a certain sense, the high water absorption and hygroscopicity of polyimide resins is a fatal drawback. For this reason, with conventional photosensitization techniques, it has not been possible to solve the problem of poor storage stability, in which moisture is absorbed when left after exposure and cracks occur during development.

However, in the present invention, by using a special photosensitive agent, not only the sensitivity was improved, but also a good pattern without cracks could be obtained.

Furthermore, it also had excellent heat resistance as a polyimide resin, as well as low elastic modulus and high adhesion due to silicone modification.

Claims (1)

[Claims] (1) Copolymerization of 0.5 to 25% by weight of silicone diamine represented by the following formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼・・・[I] (n: 1 to 50 in the formula) Polyamic acid (A) represented by the following formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... [II] (In the formula, R_1, R_2: aromatic cyclic group n: 1 to 2, m : 0 to 2), there are diacrylamide compounds (B) represented by the following formula [III] ▼ Numerical formulas, chemical formulas, tables, etc. ▼... [III] (In the formula, R_3: -H, -CH_3 R_4, R_5: -H, -CH_3, -CH_2OH)
is an essential component, and (B) 2 for 100 parts by weight of (A)
A photosensitive resin composition containing 0 to 200 parts by weight and, if necessary, a sensitizer and/or an initiator.