JPH03206452A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive polyimide resin composition good in adhesiveness, small in elasticity, high in sensitivity and heat resistance by forming the composition composed essentially of a specified polyamic acid, a specified polyfunctional acrylate, a specified biscoumarin compound, and a specified glycine compound specified in each proportion. CONSTITUTION:This composition contains the polyamic acid A obtained by copolymerizing the silicone type diamine represented by formula I in an amount of 1 - 50 wt.%; the polyfunctional acrylate B having >= 2 molecules of acrylate or methacrylate and a molecular weight of <= 500; the biscoumarine compound C substituted by a carbonyl group at its 3-position represented by formula II; and the glycin compound D represented by formula III in a proportion by weight of A : B : C : D = 100 : 20 - 200 : 1 - 10 : 1 - 20. In formulae I - III, (n) is 1 - 50; each of R1 and R2 is H, alkoxy, or dialkylamino; and R3 is H, methyl, ethyl, phenyl, or the like, thus permitting the obtained photosensitive resin composition to be enhanced in adhesion, and reduced in elasticity, but superior in photosetting performance with high sensitivity and superior in heat resistance of the hardened film.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photosensitive polyimide resin composition that has good adhesion, low elastic modulus, high sensitivity, and high heat resistance.

(Conventional technology) Conventionally, surface protection films and interlayer insulating films of semiconductor elements, etc.
Polyimide resin is used because it has excellent heat resistance and outstanding electrical and mechanical properties. With the shift to surface mounting methods using solder reflow, there is a demand for significant improvements in heat cycle resistance, heat shock resistance, etc., and conventional polyimide resins have
It has become difficult to respond.

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.

The use of polyimide resins with these photosensitizers not only has the effect of simplifying the pattern creation process compared to polyimide resins without photosensitivity, but also has the effect of simplifying the pattern creation process, but also because of the highly toxic 27
Since it does not require the use of tinde liquid, it is safe and environmentally friendly. 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 by the following formula (R.・Kyo, R5・-io-O-o-) (Tokuko Showa) Publication No. 55-30207, Special Publication No. 55-414
22) or the following formula (R1 Megumi, R7: -
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 a structure as shown by o-0-'D-). Assembled materials (e.g. Japanese Patent Application Laid-Open No. 54-1457)
Publication No. 94) and the like are known.

All of these are dissolved in a suitable organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and then heat-treated to form a 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 silicone groups have been introduced into the polyimide resin, it is difficult to buttern even when irradiated with ultraviolet rays, or the sensitivity is extremely low. It was too low to be processed by exposure equipment commonly used in the semiconductor industry.

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.

(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 high sensitivity photocurability despite lowering the elastic modulus. It is an object of the present invention to provide a photosensitive resin composite having the following properties and further having an excellent heat resistance of the film after curing.

(Means for Solving the Problems) The present invention provides a polyamic acid (A) containing 1 to 50% by weight of a silicone diamine represented by the following general formula [I].
, a polyfunctional acrylate (B) having two or more acrylic or methacrylic groups in one molecule and a molecular weight of 500 or less as a photosensitizer, and a vistamarin compound (C) represented by the following general formula [■] as a sensitizer. ) n and a glycine compound (D) represented by the following general formula (III) as an initiator as essential components, 100 parts by weight of (A), 20 to 200 parts by weight of photosensitizer (B), and a sensitizer (C). ) 1~1
0 parts by weight and 1 to 20 parts by weight of the initiator (D) are used.

(Function) The silicone diamine represented by the general formula (1) 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 when n is less than 1, the adhesion is improved,
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 tends to cause cracks.

The amount of silicone diamine used is preferably 1 to 50% by weight based on the polyamic acid content.

If it is less than 1% by weight, the effects of improving adhesion and lowering the elastic modulus cannot be obtained, and if it exceeds 50% by weight, the heat resistance is significantly reduced and the characteristics inherent to polyimide resins cannot be obtained, which is not preferable.

As the diamine used in the present invention, in addition to the above-mentioned silicone diamines, aromatic diamines such as those listed below can also be used to impart various properties.

For example, m-phenylene diamine, ①-ingrobyl-2,4-phenylene diamine, p-phenylene diamine, 4,4'-cyaminodiphenylpropane, 3.
3'-diaminodi7enylpropane, 4.4'-diaminodiphenylethane, 3.3'-diaminodiphenylethane, 4.4'-diaminodiphenylmethane, 3
．． 3'-Diaminodiphenylmethane, 4.4'-diaminodiphenylsul7ide, 3.3'-diaminodi7enylsul7it', 4.4'-cyaminodiphenylsulfone, 3.3'-cyamino diphenyl sulfone, 4.4'-diaminodiphenyl ether, 3.3'
-Diamino-di7enyl ether, benzidine, 3.3
'-Diaminobi-7enyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3.3'-dimethoxybenzidine, 4.4''-diaminop-terphenyl,
3.3”-diamino-p-terphenyl, bis(p-aminosichexyl)methane, bis(p-β-amino-t-butyl7enyl)ether, bis(p-β-methyltoaminopentyl)benzene, p -bis(2-methyl-4-aminopentyl)benzene, p-bis(1.
1-dimethyl-5-aminopentyl)benzene, 1.
5-diaminona7talene, 2.6-diaminonaphthalene, 2.4-bis(β-amino-t-phthyl)toluene, 2.4-diaminotoluene, m-xylene-2.
5-diamine, p-xylene-2,5-diamine, m-
xylylene diamine, p-xylylene diamine, 2
．． 6-diaminorpyridine, 2,5-diaminorpyridine, 2,S-diamino-1.3.4-oxadiazole, 1,4-diaminor/Yuguchihexane, piperazine, methylenediamine, ethylenediamine, Flopylene diamine, 2,2-dimethyl-propylene diamine,
Tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2,5-dimethyl hexamethylene diamine, 3-methoxyhexamethylene diamine, heptamethylene diamine, 2,5-dimethyl hexamethylene diamine , 3-methyl-hebutamethylene-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, 2.11-diaminodecane, 1.1
Examples include, but are not limited to, 2-diamino-octadecane, 2,12-diamino-octadecane, and 2,17-diamino-icosane.

The tetracarboxylic dianhydride component to be reacted with the diamine dianhydride 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
'-penzophenonetetracarboxylic dianhydride, 2.2
'． 3.3'-benzophenonetetracarboxylic dianhydride, 2.3.3'. 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2.3.6.7-
Carponic dianhydride, naphthalene-1.2,5
．． 6-tetracarboxylic dianhydride, naphthalene-1.2
, 4.5-tetracarboxylic dianhydride, naphthalene-1
．． 4,5.8 Tetracarboxylic dianhydride, Na7talene
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-hexahide naphthalene-2.3.6.7-tetracarboxylic dianhydride, 2,6-dichlorona7talene-1,4,5.
8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,3.6.7-tetrac-naphthalene-1.4,5
．． 8-Tetracarboxylic dianhydride, 1,4,5.8-tetracarboxylic naphthalene-2.3,6,7-tetracarboxylic dianhydride, 3.3',4.4'-diphenyltetracarboxylic acid Dianhydride, 22',3.3'-diphenyltetracarboxylic dianhydride, 2,3.3',4'
-diphenyltetracarboxylic dianhydride, 3.3".
4.4"-p-tel7enyltetracarboxylic dianhydride, 2.2", 3.3"-p-tel7enyltetracarboxylic dianhydride, 2,3.3",4" -p
-Terphenyltetracarboxylic dianhydride, 2.2-bis(2.3-dicarpoxyphenyl)-propanihydride, 2.2-bis(3.4.-dicarpoxyphenyl)
monopropanihydride, bis(2,3-dicarpoquinphenyl)ether dianhydride, bis(3.4-dicarpoxo-7enyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis (3l4-dicarpoxyphenyl)methane dimhydrate,! :'su(2.3-
dicarboxyphenyl) sulfone dianhydride, bis(3.
4-dicarpoxyphenyl)sulfonic anhydride, l,1
-Bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarpoxyphenyl)ethane dianhydride, perylene-2.3,8.9-tetracarboxylic dianhydride, perylene -3.49.10-tetracarboxylic dianhydride, perylene-4.5,10.11-tetracarboxylic dianhydride, perylene-5.6.11.1
2-tetracarboxylic dianhydride, phenanthrene-1.
2,7.8-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, Examples include, but are not limited to, 4,5-tetracarboxylic dianhydride.

In the present invention, (B) the polyfunctional acrylate for ff is 1
It is an acrylic compound having a molecular weight of 500 or less and having two or more acrylic or methacrylic groups in the molecule.

Monofunctional acrylates having one acrylic group in one molecule are not preferred because they cannot be photopatterned because a crosslinked structure cannot be obtained even when irradiated with light.

In addition, if the molecular weight is 500 or more, it is not only difficult to uniformly dissolve the polyimide, but also it remains in the polyimide film without being dissipated even during heat treatment for thermosetting, resulting in a marked decrease in heat resistance, which is preferable. do not have.

As the polyfunctional acrylate (B), ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1.6-hexanediacrylate,
1.6-hexanediol dimethacrylate, neopentyl glycol diacrylate, inopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, trimethylolpropane triacrylate, trimethylolfuropane trimethacrylate, Examples include, but are not limited to, bisphenol A dimethacrylate.

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 the amount is less than 20 parts by weight, a sufficient photocrosslinked product will not be obtained and will all dissolve during development, which is not preferred.

Moreover, if the blending amount exceeds 200 parts by weight, the added amount is so large that even if photocrosslinking is effected, scattering shrinkage will be large during heat treatment and cranking will easily occur, which is undesirable.

The sensitizer (C) in the present invention is a vistamarin compound substituted with carbonyl at the 3-position represented by the following formula [■] n (in the formula, R, , R2: -H, an alkoxy group, a dialkylamino group) It is.

Examples of the biscoumarin compound include 3.3' carbonyl rubis (7-diethylaminocoumarin), 3.3
Examples include, but are not limited to, carbonyl coumarin (5J-dimethoxyluponyl coumarin).

Sensitizers used in photosensitive resin compositions include penzophenone, acetophenone, anthrone, plp'-tetramethyldiaminobenzophenone (Michler's ketone),
7-enanthrene, 2-nitrophnoleolelene, 5-nitroacenaphthene, pensoquinone, N-acetyl-p-nitroaniline, p-nitroaniline, 2-ethynoleanthraquinone, 2-ternarybutynoleanthraquinone,
N-acetyl-4-nitro-1-na7thylamine, picramide, 1,2-penzanthraquinone, 3-methyl-
1.3-Diazor 1.9-Penzuanthrone, p. p
'-Tetraethynolediaminobenzophenone, 2-chloro-4-nitroaniline, cypenzalacetone, 1.2
-naphthoquinone, 2,5-bis-(4'-diethylaminobenzanole)-cyclopentane, 2,6-hisu(4
'-diethylaminobenzal)-cyclohexanone, 2
．． 6-bis-(4'-dimethylaminobenzal)-4-methyl-cyclohexanone, 2,6-bis-(4'-diethylaminobenzal)-4-methyl-cyclohexanone, 4,4'-bis-(dimethylamino) ) one chalcone,
4.4'-bis-(diethylamino)monochalcone, p-
Dimethylaminobenzylideneindanone, 1.3-bis-(4'-dimethylaminobenzal)monoacetone, 1.
Examples of the vistamarin compound discovered in the present invention include 3-bis(4'-diethylaminobenzal)mona7ton, N-7enyludiethanolamine, and N-1)-tolyludiethylamine. Only when used in combination with the glycine compound used as an initiator in the present invention does a surprisingly excellent sensitizing effect occur. The reason for this surprising synergistic effect is not yet clear.

The amount of Vistamarin compound is 1 part polyamic acid.
The most preferable amount is 1 part by weight or more and 10 parts by weight or less per 00 parts by weight, and sensitizers other than the vistamarin compound may also be used in combination.

When the amount of Vistamarin compound is less than 1M part,
If the amount of absorption of photonic energy is insufficient, crosslinking will be insufficient, and if the loft amount is exceeded, the amount of light energy transmitted will be insufficient, and photocuring in deep portions will not proceed quickly, which is not preferable.

The initiator (D) in the present invention has the following formula [■] (in the formula, R 3 : -H , -C H s, -C 2H S
, -C 6H S. OCHx, -00CCHx, -OC
zHa. 00CCzHs, -N(CHs)z, -N(C
zHs)z, -NHCOOCHs, -COCHs, -COC2Hs, -NHCONH 2, -CH20H-
OH, -CH(CH3)! , -C(CH3)3) is a glycine compound with a phenyl group.

Initiators used in photosensitive resin composites include 2.2-
Dimethoxy-2-7enyl-acetophenone, I-hydroxy-cyclohexyl-7enylketone, 2-methynole[4-(methynolethio)phenol]-2-monolyl-linol-propane, 3.3'4.4'-tetra (t-butylperoxycarbonyl)penzophenone, benzyl, penzoin-impyl ether, 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'-tetra7enyl l. 2'-biimidazole, 10-butyl-2-chloroacridone, ethyl-4-dimethylaminobenzoate, dibenzoylmethane, 2,4-diethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, l-(4-improbyl-7enyl)-
2-Hydroxy-2-methylpropan-1-one, I-
(4-dodecylphenyl)-2-hydroxy-2-methylbroban-1-one, l-7enyl-1,2-butanedione-2-(o-methoxyluponyl)oxime,
1-7enylpropanebutanedione-2-(o-benzoyl)oxime, 1,2-diphenyluethanedione-1-(o-benzoyl)oxime, X,3-cyphenylupropanetrione-2-(o -benzoyl)oxime, I-7enyl-3-ethoxypropanetrione-2(0-benzoyl)oxime, etc., but the glycine compound discovered in the present invention is vistamarin as a sensitizer. When combined with a compound, it showed a remarkable photoreaction initiation effect compared to other initiators.

The reason for how this surprising effect is expressed is currently not clear.

The composition of the glycine compound is polyamic rI1.
It is essential to use 1 to 20 parts by weight per 100 parts by weight, and initiators other than glycine compounds may also be used in combination.

If the amount of glycine compound as an initiator is less than 1 part by weight, the photosensitivity will be insufficient, which is not preferable.

Moreover, if it exceeds 20 parts by weight, the film properties after heat treatment and curing will deteriorate.

The present invention will be specifically explained below using Examples.

Example 1 Silicone diamine with 15 siloxane bonds (n=
15) of the following formula (35% by weight in polyamic acid), 45 g of 3,3'',4.4'-benzophenonetetracarboxylic dianhydride, and 20 g of 4,4'-diaminodiphenyl ether. 60 g (60 g parts) of 1,4-butanediol dimethacrylate and 3.3'-carbonyl rubis (7-jet. tylaminocoumarin) 4g (4 parts by weight)
and 8 g (8 parts by weight) of N-phenyl green were added and mixed and dissolved at room temperature.

The obtained solution was applied onto an aluminum plate using a swinner and dried at 80°C for 1 hour using a drier.

This film is coated with Kodak Photographic Step Tablet No.2.
J2, so the larger the residual stage after development, the better the sensitivity. When further rinsed with Inglobil alcohol, the pattern remained up to 14 steps, indicating high sensitivity.

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

For the adhesion test, I cut it into 1mm square pieces and tried to peel it off with a cellotape, but not a single piece came off, indicating that it had high adhesion.

Well, it is coated separately on an aluminum plate, exposed to light on the entire surface, developed, rinsed, and heat cured, then the aluminum plate is removed by etching.
I got 7 ilms.

Tensile modulus of the obtained film (JIS K-6760
) was as small as 100 Kg/mm'', and the thermal decomposition onset temperature was as high as 440°C.

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

Comparative Example 1-13 A similar experiment was carried out according to the method of Example 1, changing the number of siloxane bonds in the silicone diamine, the amount added, and the type and amount of the photosensitizer, sensitizer, and initiator, and the results shown in Table 1 were obtained. Obtained.

In Comparative Example 1, the amount of initiator added was 0.8 parts by weight (I), and the photosensitivity was extremely low.

Comparative Example 2 is the opposite of Comparative Example 1, with 28 parts by weight.
In this case, the initiator remained in the film, resulting in a low thermal decomposition initiation temperature.

Comparative Example 3 used an initiator other than the one according to the invention, had low photosensitivity, and was not practical.

In Comparative Example 4, the amount of sensitizer added was 0.4 parts by weight, and in this case, the photosensitivity was extremely low and the crosslinking was insufficient.

In Comparative Example 5, the amount of sensitizer was 24 parts by weight, and in this case, the amount of light transmitted to the deep part was insufficient, the curing in the deep part was insufficient, and voids were generated, and a uniform film was not obtained.

Comparative Example 6 used a sensitizer other than the one according to the invention and had low photosensitivity, making it impractical.

In Comparative Example 7, the amount of photosensitizer added was 15 parts by weight,
In this case, not only was the photosensitivity low, but also the film loss was large due to insufficient crosslinking.

In Comparative Example 8, the amount of photosensitive agent added was 250 parts by weight, and in this case, there was a large amount of stray grains during high temperature curing, cracks occurred, and a uniform film could not be obtained.

Comparative Example 9 used a photosensitizer other than the one of the present invention, and since it was a monofunctional acrylate, it did not become three-dimensional even after exposure, and all of it washed away during development.

In Comparative Example 10, the amount of silicone diamine added was 0.5% by weight, and in this case, the elastic modulus could not be lowered.

In Comparative Example 11, the amount of silicone diamine added was 70% by weight.
In this case, the film became blurred.

In Comparative Example 12, the number of siloxane bonds in the silicone diamine was set to n=o, and in this case, cracks occurred during film formation due to lack of flexibility.

In Comparative Example 13, the number of siloxane bonds in the siloxane diamine was n-too, and in this case, the reactivity was low, unreacted silicone was exposed at the time of film formation, and the sensitivity was not improved.

(Effects of the Invention) Attempts have been made to improve adhesion and reduce elastic modulus by introducing siloxane bonds into the main chain structure of polyimide resins.

However, with conventional photosensitization techniques, it has not been possible to obtain good patterns because there are no suitable sensitizers or initiators to improve the photosensitivity of silicone-modified polyimide resins.

However, in the present invention, by employing a combination of a special sensitizer with extremely high photosensitivity and an initiator, it has become possible to obtain a good pattern with a small amount of light irradiation. Furthermore, the heat-cured polyimide resin has excellent heat resistance as all the photo-cured acrylates scatter, and since it has been modified with silicone, it has a low elastic modulus and high adhesion. I got it at the same time.

Claims (1)

[Claims] (1) (A) Polyamic acid containing 1 to 50% by weight of silicone diamine represented by the following formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ---- [ I ] (In the formula, n is 1 ~50) (B) A polyfunctional acrylate having two or more acrylic or methacrylic groups in one molecule and having a molecular weight of 500 or less (C) A biscoumarin compound substituted with carbonyl at the 3-position represented by the following formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼−−−−−−−[I
I] (In the formula, R_1, R_2: -H, alkoxy group, dialkylamino group) (D) Glycine compound represented by the following formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ ------- [III] (R_3 in the formula: -H, -CH_3, -C_2H_5, -
C_6H_5, -OCH_3, -OOCCH_3, -O
C_2H_5, -OOCC_2H_5, -N(CH_3
)_2, -N(C_2H_5)_2, -NHCOOCH
_3, -COCH_3, -COC_2H_5, -NHCONH_2, -CH_2
OH-OH, -CH(CH_3)_2, -C(CH_3
)_3) is an essential component and (A) is (100 parts by weight) (
B) 20 to 200 parts by weight, (C) 1 to 10 parts by weight, and (
D) A photosensitive resin composition comprising 1 to 20 parts by weight.