JPH0350787B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition that can form a heat-resistant thin film and is sensitive to light such as ultraviolet rays, deep ultraviolet rays, and electron beams, or to ionizing radiation. Polyimide resin has conventionally been known as a polymer compound with excellent heat resistance, and in order to take advantage of this excellent heat resistance, a composition forming polyimide resin that is photosensitive and suitable as, for example, a photoresist material is used. Research has been carried out to obtain suitable materials. For example, a photosensitive resin composition is known in which dichromate is added to a polar solvent solution of polyimide acid, which is a precursor of polyimide resin (Polymer Engineering and Science 11 426
(1971)). Although this photosensitive resin composition has advantages such as having practical photosensitivity, being able to be developed with water, and having a high film-forming ability and being relatively easy to form a thin film, it is difficult to form a final film. dichromate remains in the cured polyimide resin, resulting in a decrease in electrical insulation; a dark reaction occurs, resulting in a lack of storage stability; and wastewater from the manufacturing process contains hexavalent chromium. Therefore, there were problems such as the need for pollution treatment. On the other hand, a photosensitive resin in which a photosensitive group has been introduced into polyamic acid, such as pyromellitic anhydride, is reacted with a compound having a photosensitive group and a hydroxyl group such as 2-hydroxyethyl methacrylate, and then thionyl chloride is used to react the photosensitive resin with a photosensitive group. Polyamic acid, which is obtained by obtaining a dibasic acid chloride compound with a pyromellitic acid structure and introducing a photosensitive group obtained by polycondensing this with an aromatic diamine (Polymer
Engineering and Science 15 92 (1976)). Such photosensitive resins not only have a complicated manufacturing process, but also involve a dehydrochloric acid reaction at the stage of introducing the photosensitive group, which ultimately results in hydrochloric acid remaining in the polyamic acid, resulting in poor performance in semiconductor devices. When applied to electronic parts such as, the presence of chlorine ions causes corrosion of the electronic parts, so it is not necessarily a preferable photosensitive resin. Furthermore, as a photosensitive resin composition that has improved such drawbacks, a composition in which an aromatic bisazide compound, orthoquinonediazide, or naphthoquinonediazide is added to polyamic acid, which is a precursor of fully aromatic polyimide, has been proposed (Japanese Patent Application Laid-Open No. 127723-1989). No. 52-13315) are known, and it is known that both of these have the advantage of not producing corrosive free ions. However, polyamic acid, which is the precursor of these aromatic polyimides, generally has poor storage stability, with problems such as a decrease in molecular weight and precipitation of insoluble matter when stored at room temperature, and is not stable even when stored at low temperatures. It has the disadvantage that it can be stored for a very short period of time. As a result of intensive research to improve the above-mentioned drawbacks, the present inventors have found that polyamic acid obtained from a specific tetracarboxylic acid or its anhydride and a diamine compound has a crosslinking reaction activated by light or ionizing radiation. A resin composition containing a compound that generates seeds has excellent storage stability, high sensitivity to light or ionizing radiation, high resolution, and excellent adhesion to substrates. The present invention was completed based on the discovery that That is, the object of the present invention is to provide excellent storage stability;
highly sensitive to light or ionizing radiation;
The object of the present invention is to provide a resin composition that provides high resolution and has excellent film-forming ability and adhesiveness to substrates and the like. The present invention is characterized in that it contains a polyamic acid obtained from an alicyclic tetracarboxylic acid or its anhydride and a diamine compound, and a compound that generates a crosslinking reaction active species when exposed to light or ionizing radiation. It is in. The present invention will be specifically explained below. In the present invention, polyamic acid is obtained by reacting at least one selected from alicyclic tetracarboxylic acids and their anhydrides with a diamine compound, and this is subjected to a crosslinking reaction with light or ionizing radiation. A resin composition is obtained by adding a compound that generates active species. Specific examples of alicyclic tetracarboxylic acids or anhydrides thereof used in the present invention include 1, 1, 2,
2-cyclopropanetetracarboxylic acid, 1,2,
3,4-cyclobutanetetracarboxylic acid, 1,
2,3,4-cyclopentanetetracarboxylic acid,
Examples include 1,2,3,4-cyclohexane-tetracarboxylic acid, 2,3,5-tricarboxy-cyclopentyl acetic acid, methylcyclohexenetetracarboxylic acid, anhydrides thereof, and others. As described above, by using the alicyclic tetracarboxylic acid or its anhydride, the adhesiveness of the resin composition of the present invention to a substrate or the like can be increased. Note that when an anhydride of tetracarboxylic acid is used, a dianhydride is usually used. Further, the diamine compound which reacts with the above-mentioned tetracarboxylic acid or its anhydride to give polyamic acid is a compound represented by the general formula H ₂ N-R-NH ₂ (R is a divalent aromatic group or an aliphatic or aliphatic group). cyclic hydrocarbon group). Preferred R in the above general formula is, for example,

【formula】

【formula】

[Formula] (wherein, X ₁ , X ₂ , X ₃ and X ₄ are the same or different and are H or CH ₃ , and Y is CH ₂ , C ₂ H ₄ , O,
S, C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ or CONH, and n represents 0 or 1. ), such as -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -
(CH ₂ ) ₄ −, −(CH ₂ ) ₅ −, −(CH ₂ ) ₆ −, −(CH ₂ ) ₇
−, −(CH ₂ ) ₈ −,

【formula】

【formula】

【formula】

[Formula] It is an aliphatic or alicyclic hydrocarbon group having 6 to 13 carbon atoms or a norbornane derivative hydrocarbon group, and the heat resistance when the composition of the present invention is imidized by heat treatment. In order to further improve the properties, R is preferably an aromatic group. Specific examples of the above diamine include paraphenylenediamine, metaphenylenediamine, 4,4'-
Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 2,2-di(P-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylpropane, benzidine, 4,4'-diaminodiphenyls Ruphid, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-
Dimethyl-4,4'-diaminobiphenyl, 3,
4'-Diaminobenzanilide, 3,4'-diaminodiphenyl ether, metaxylylene diamine and paraxylylene diamine, ethylene diamine, propane diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene Diamine, nonamethylene diamine, 4,4'-dimethylheptamethylene diamine, 1,4-diaminocyclohexane, tetrahydrodicyclopentadienyl diamine, hexahydro-4,7-methanoindani dimethylene diamine, tricyclo[6,2 , 1,0 ^2.7 ]-undecylenedimethyldiamine, and the like. These can be used alone or in combination. The solvent for the reaction to obtain polyamic acid is preferably one that dissolves both tetracarboxylic acid or its anhydride and diamine compound in order to increase the molecular weight of polyamic acid, and specifically N-methyl-2-pyrrolidone. , N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphortriamide, and other aprotic dipolar polar solvents are preferred, but alcohols, which are common organic solvents, are preferred. phenols, ketones,
Ethers such as ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, phenol, cresol, methyl ethyl ketone, tetrahydrofuran, etc. can also be used. The amount of these solvents used is generally 0.5 to 20 times the weight of the tetracarboxylic acid or its anhydride and the diamine compound. The reaction ratio of the above-mentioned tetracarboxylic acid or its anhydride and the diamine compound is preferably carried out in equimolar amounts, but as long as the object of the present invention is achieved, there may be a slight excess or deficiency. In order to obtain a high molecular weight polyamic acid, the diamine compound is usually used in an amount of about 0.7 to 1.3 moles per mole of the tetracarboxylic acid or its anhydride. The reaction temperature when producing polyamic acid differs depending on whether tetracarboxylic acid or tetracarboxylic acid anhydride is used as the starting material; if tetracarboxylic acid is used as the starting material, dehydration condensation is performed. Normally 50-300℃, preferably 100-250℃
It is effective to carry out the reaction with On the other hand, when tetracarboxylic acid anhydride is used as a raw material, addition polymerization is performed, and the reaction does not necessarily need to be carried out at a high temperature; it is usually sufficient to carry out the reaction at a temperature of 0 to 100°C. The polyamic acid obtained in the above manner is
Usually, it is used after being purified and redissolved in a solvent, but depending on the use of the composition of the present invention, the solution after the reaction can be used as it is. In addition, examples of the solvent for redissolving polyamic acid include the aforementioned aprotic solvents, dipolar polar solvents, alkaline aqueous solutions, and the like. In addition, the reduced viscosity of polyamic acid (ηSP/C, C=1g/100ml,
N,N'-dimethylacetamide) is preferably 0.05 dl/g or more, particularly preferably 0.05 to 5 dl/g.
It is g. Examples of crosslinking active species in the compound that generates crosslinking active species include carbene, radical,
Examples include nitrene. Examples of compounds that generate carbene as a crosslinking reaction active species include P-quinonediazide compounds such as P-benzoquinonediazide and P-naphthoquinonediazide; examples of compounds that generate radicals as a crosslinking reaction species include diacetyl, benzoin, etc. Compounds that generate nitrene as crosslinking reaction active species include carbonium compounds, azo compounds such as azobisisobutyronitrile, and organic sulfur compounds such as mercaptan disulfide.
4,4'-diazidostilbene, sodium 4,4'-diazidostilbene-2,2'-disulfonate,
1,5-diazidnaphthalene, sodium 1,5-diazidnaphthalene-3,7-disulfonate,
4,4'-Diazidobenzophenone, 4,4'-diazidodiphenylmethane, 4,4'-diazidochalcone, 4,4'-diazidobenzalacetone, 2,6
-di(4′-azidobenzal)cyclohexanone,
2,6-di(4'-azidobenzal)-4-methylcyclohexanone, 6-azido-2-(4'-azidostyryl)benzimidazole, 2,6-di(4'-azidobenzal)cyclopentanone, 4,
4'-Diazidobiphenyl, 3,3'-Diazidobiphenyl, 4,4'-Diazidophenylmethane, 3,
3'-Diazidiphenylmethane, 4,4'-Diazidiphenyl ethane, 3,3'-Diazidiphenyl ethane, 4,4'-Diazidiphenyl ether,
3,3'-Diazidophenyl ether, 4,4'-Diazidiphenyl sulfide, 3,3'-Diazidiphenyl sulfide, 4,4'-Diazidiphenyl sulfone, 3 , 3'-diazide diphenyl sulfon and other aromatic bisazide compounds. The amount of the compound that generates crosslinking active species when exposed to light or ionizing radiation is preferably 0.5 to 30 parts by weight per 100 parts by weight of polyamic acid. Since the resin composition of the present invention is as described above, it has excellent storage stability compared to conventional polyamic acid-based photosensitive resin compositions, as will be understood from the explanation of the examples below. obtain a film body that has high sensitivity to light or ionizing radiation, high resolution, high film-forming ability, easy to form a thin film, and high adhesion to substrates, etc. Therefore, it is extremely suitable as, for example, a resist material or an electrical insulating material. The reason why the above excellent effects can be obtained is as follows.
Although it is not necessarily clear, when comparing the crosslinking properties of alicyclic tetracarboxylic acids or their dianhydrides and aromatic tetracarboxylic acids or their dianhydrides with bisazide compounds, it is found that -C- of aromatic hydrocarbons
Alicyclic tertiary or secondary - than H bond
The crosslinking reactivity due to the crosslinking active species in the C-H bond is higher, and the number of bonds is large, so
The fact that the polyamic acid used in the present invention has an advantageous effect on crosslinking and has an excellent adhesive force as described above is superior to, for example, a photosensitive resin composition made of a conventional wholly aromatic polyamic acid. This is considered to be part of the reason why it is possible to express such characteristics. In order to use the composition of the present invention as a resist material, for example, a compound that generates a crosslinking reaction active species by light or ionizing radiation as described above is dissolved in a solution of the polyamic acid described above, and a resist film is formed with this solution. do it. That is, a solution of the resin composition of the present invention is applied to a substrate such as an aluminum plate, a glass plate,
Bimetal plates, ceramic plates, semiconductor wafers,
It is applied to the surface of a printed circuit board or the like by a technique such as spin coating, and prebaked at a temperature of 100 to 150°C to remove the solvent in the film and form a uniform film. Then, light or ionizing radiation is selectively irradiated through a photomask having a desired image, and then developed with a developer, whereby the exposed portion remains insoluble and a pattern is formed. Examples of the developer include N,N-dimethylacetamide, N-methyl-2-pyrrolidone,
Single or mixed solvents such as N,N-dimethylformamide, tetramethylurea, hexamethylphosphoramide, and dimethyl sulfoxide can be used, but these solvents may be further mixed with a poor solvent such as methanol, ethanol, propanol, or acetone. By doing so, it is also possible to obtain a developer whose development time is appropriately adjusted. Furthermore, aqueous ammonia or aqueous solutions of primary amines, secondary amines, and tertiary amines can also be used as the developer. Even in this case, the development time can be adjusted to an appropriate value by changing the alkali concentration. After development, the film is rinsed with a poor solvent, dried, and heat-treated at a temperature of 200 to 400°C to imidize, thereby forming a heat-resistant polyimide film. Therefore, this coating has great durability. The resin composition of the present invention can be used not only as a resist material for heat-resistant patterns, but also as a passivation film for semiconductor devices, a multilayer wiring insulating film, a junction protective film, a lift-off mask material, an alpha ray shielding film, and an interlayer insulation film for highly integrated electronic circuits. membrane, ion implantation mask,
Although it is particularly useful as an electronic material such as a protective film for electronic circuits, its uses are not limited to these. The present invention will be explained below with reference to Examples. Example 1 Polyamic acid obtained from 2,3,5-tricarboxycyclopentyl acetic acid and 4,4'-diaminodiphenyl ether (ηSP/C=1.57 dl/g,
C=1g/100ml, temperature in dimethylacetamide
Add and dissolve 5 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone per 100 parts by weight of polyamic acid into a dimethylacetamide solution (polyamic acid concentration 12% by weight) at 30℃). A resin composition of the present invention was produced. Spread this liquid onto the surface of the aluminum substrate for 2000r.
After spin coating under pm conditions, prebaking was performed at a temperature of 140°C for 10 minutes to form a uniform film.
Then, light from a high-pressure mercury lamp is passed through a photomask with a mask hole width of 0.2 to 1.0 mm for resolution measurement.
The film was irradiated with light energy of 500 mJ/cm ² , developed with dimethylacetamide, rinsed with acetone, and then heat-treated at 300° C. for 30 minutes to carry out an imidization reaction and harden the film. The resulting pattern of the polyimide coating had no pinholes and was a clean pattern even with thin lines from 1.0 mm to 0.2 mm, and when observed under a microscope, it was observed that the edges were also sharp. Further, even when the above composition was stored at room temperature for 3 months, no decrease in molecular weight or precipitation of insoluble matter was observed. The polyimide film obtained from the composition after storage also had sufficient heat resistance. Experimental Example 1 In order to evaluate the adhesion of the polyimide film obtained from the composition obtained in Example 1 to a substrate, a peel test using an adhesive tape was conducted. That is, a polyimide film formed under the same conditions as in Example 1 was cut vertically and horizontally with a cutter to form 25 2 mm square pieces, 5 in each direction, and an adhesive tape was injected into the pieces. The number of pieces that were peeled off by the adhesive tape among the 25 pieces was determined by crimping the pieces so that they would not get stuck and then peeling them off. When the adhesion was evaluated based on the ratio of the number of pieces that remained without being peeled off to the total number of pieces, the number of pieces that were peeled off was 0, and the adhesiveness was evaluated as 1. Comparative Example 1 Dimethylacetamide of polyamic acid obtained from pyromellitic anhydride and 4,4'-diaminodiphenyl ether (ηSP/C=1.44 dl/g, C=1 g/100 ml, in dimethylacetamide, temperature 30°C) A resin composition was produced, coated, exposed, developed, and heat treated in the same manner as in Example 1, except that a solution (polyamic acid concentration: 12% by weight) was used. When we investigated the resolution of the pattern after development and heat treatment, we found that the pattern portion smaller than 0.8mm was
I couldn't resolve it. In addition, pinholes were observed in the film after curing. Furthermore, the edge of the pattern was less sharp than in Example 1. On the other hand, when the solution of the resin composition was stored at room temperature, a decrease in molecular weight was observed within several days. Further, the same peeling test as in Experimental Example 1 was carried out on the film obtained in Comparative Example 1, and its adhesiveness was evaluated. The number of peeled pieces was 9, and the adhesiveness was evaluated as 0.64. Example 2 1,2,3,4- instead of 2,3,5-tricarboxycyclopentyl acetic acid in Example 1
Polyamic acid obtained using cyclobutanetetracarboxylic dianhydride (ηSP/C=1.08
dl/g, C = 1 g/100 ml, in dimethylacetamide, temperature 30°C), 5 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone was added and dissolved. A resin composition of the present invention was produced. When this resin composition was evaluated for photosensitivity and storage stability in the same manner as in Example 1, good results similar to those of the resin composition of Example 1 were obtained. Example 3 1,2,3,4- instead of 2,3,5-tricarboxycyclopentyl acetic acid in Example 1
Polyamic acid obtained using cyclopentanetetracarboxylic dianhydride (ηSP/C=1.43
dl/g, C = 1 g/100 ml, in dimethylacetamide, temperature 30°C), 5 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone was added and dissolved. A resin composition of the present invention was produced. When this resin composition was evaluated for photosensitivity and storage stability in the same manner as in Example 1, good results similar to those of the resin composition of Example 1 were obtained. Example 4 1,2,3,4- instead of 2,3,5-tricarboxycyclopentyl acetic acid in Example 1
Polyamic acid obtained using cyclohexanetetracarboxylic dianhydride (ηSP/C=1.27
dl/g, C = 1 g/100 ml, in dimethylacetamide, temperature 30°C), 5 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone was added and dissolved. A resin composition of the present invention was produced. When this resin composition was evaluated for photosensitivity and storage safety in the same manner as in Example 1, good results similar to those of the resin composition of Example 1 were obtained. Example 5 Using methylcyclohexenetetracarboxylic dianhydride in place of 2,3,5-tricarboxycyclopentyl acetic acid in Example 1, the obtained polyamic acid (ηSP/C=1.39 dl/g, C=
1g/100ml in dimethylacetamide, temperature 30
The resin composition of the present invention was prepared by adding and dissolving 5 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone to 100 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone. When this resin composition was evaluated for photosensitivity and storage stability in the same manner as in Example 1, good results similar to those of the resin composition of Example 1 were obtained. Example 6 Polyamic acid (ηSP/C=1.65
dl/g, C = 1 g/100 ml, in dimethylacetamide, temperature 30°C), 5 parts by weight of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone was added and dissolved. A resin composition of the present invention was produced. When this resin composition was evaluated for photosensitivity and storage stability in the same manner as in Example 1, good results similar to those of the resin composition of Example 1 were obtained. Experimental Example 2 For each of the resin compositions of Examples 2 to 6, a peel test was performed on the substrate in the same manner as in Experimental Example 1 to evaluate the adhesion, and the results shown in Table 1 were obtained. .

[Table] From the above results, the resin composition according to the present invention has
It can be seen that it is possible to form a heat-resistant polyimide film that has excellent storage stability, high sensitivity to light or ionizing radiation, excellent resolution, and excellent adhesion to the substrate.

Claims (1)

[Claims] 1. A resin composition comprising a polyamic acid obtained from an alicyclic tetracarboxylic acid or its anhydride and a diamine compound, and a compound that generates a crosslinking reaction active species when exposed to light or ionizing radiation.