JPH0358048A - Positive type photosensitive polyiide composition - Google Patents

Abstract

PURPOSE:To enhance solubility of an imide polymer and to reduce shrinkage of its volume after hardening by introducing specified functional groups into the molecular skeleton of the polymer. CONSTITUTION:The title composition contains the photosensitive polyimide of formula 1 in which Ar1 is an aromatic hydrocarbon group; Ar2 is an aromatic hydrocarbon residual group having an o-naphthoquinone diazidosulfonylxy group on at least one of rotho- and meta-positions; and R is H or a group of formula II and it is contained in an amount of >= 5 mol %. Ar1 can be embodied by a group of formula III, Ar2 can be embodied by formula IV, 90 mol parts of R may be H and 10 mol parts may be the groups of formula II. A photodecomposable proton-generating agent can be added to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a solid photosensitive solid straw molded article.

(Conventional technology) Polyimide is used for various electronic components due to its excellent properties such as heat resistance, electrical properties, and mechanical properties. Attempts have been made to provide this.

In particular, regarding the positive-type photosensitive polyide ξ-de, there is a method of mixing a photosensitive orthonaphthoquinone diazide compound with a polyide precursor (JP-A-52-13315), and a method of mixing a photosensitive ortho-naphthoquinone diazide compound with a soluble polyide ξ-de. A method of mixing the two has been proposed.

The above-mentioned photosensitive polyimide composite coating is usually applied in a solution state onto the substrate, dried, and after applying a photomask, is irradiated with actinic light such as ultraviolet rays. Next, the exposed area is dissolved and removed using an arbitrary developer to form a desired image.

After forming the image, a heat-resistant polyimide film is obtained by performing high temperature treatment to close the polyimide ring and volatilize and remove the solvent, ring-closing water, naphthoquinone diazide, etc.

Problems to be Solved by the Invention> However, in general, the above-mentioned conventional photosensitive composite soles only contain a polyimide precursor or polyimide mixed with orthonaphthoquinone diazide, which is a photosensitive compound, and when irradiated with light, Only orthonaphthoquinonediazide is alkali-soluble, and the structure of the polymer skeleton does not change in any way when exposed to light.

Therefore, a large amount of orthonaphthoquinone diazide must be mixed in order to improve the ability to inhibit dissolution of the unexposed area in the developing solution, resulting in volumetric shrinkage after curing and a significant drop in dimensional accuracy. The purpose of the present invention is to provide a positive photosensitive polymer ξ-doped assembly which has high photosensitivity even in the formation of fine patterns by improving the solubility of the polymer itself and has excellent dimensional accuracy. be.

As a result of extensive studies, the present inventors have discovered that the above object can be achieved by introducing a specific functional group into the molecular skeleton of an imide polymer, and have completed the present invention. I have come to admonish you.

That is, the positive type photosensitive polyimide composition of the present invention has the following general formula (1), (wherein Ar is a tetravalent aromatic hydrocarbon residue, Ar
z is a divalent aromatic hydrocarbon residue having an O-naphthoquinonediazide sulfonyloxy group at at least one ortho or meta position of the aromatic ring), and R is a di-type Photosensitive polyimide group y'
Ii. It is something that provides something.

Art in the above general formula [I] is a tetravalent aromatic hydrocarbon residue, specifically a fused polycyclic aromatic group with a benzene ring, a naphthalene ring, an anthracene ring, etc., and the following general formula: ? However, in the formula, Ph is a benzene ring, p is O or 1, and χ is preferably the following group.

-C}! Z, C (old C)! , CO
, -S--SO■1 -o-,-o-ph-s-ph
-〇1C(CF3)! , O Ph SO
x Ph 0-O Ph C(CF3)z −
F'h O ) In addition, krt in the above general formula is 0 at at least one ortho position or meta position of the aromatic ring.
-2 having a naphthoquinonediazide sulfonyloxy group
It is a valent aromatic hydrocarbon residue, specifically the following,
The aromatic hydrocarbon residue in the general formula CI) can be replaced by the combined use of 1 to 50 mol% of an aromatic diaano compound capable of introducing a residue represented by 1^r3-. can. Examples of diane for introducing ^r include 4,4'-dianodiphenyl ether, 3,3'-dimethyl-4,4゜-diaξnodiphenyl ether, 3,3'-dimethoxy4,4 Diphenyl ether type diaryons such as ゜-diaminodiphenyl ether, 3.3゜-diaminodiphenyl ether, 3,4゜-diaminodiphenyl ether, 4,4゜-diaminodiphenylthioether, 3.3'-dimethyl-4 ,4
'-diaξnodiphenylthioether, 3,3'-dimethoxy4,4-diashort diphenylthioether,
3.3'-Diphenylthioether-based diarowers such as diaminodiphnyl thioether, 4,4゜-diaξnobenzophenone, 3.3''-dimethyl-4.4゛-diaminobenzophenone, 3,3゜-dia Penzophenone diamines such as fruit benzophenone, diphenylmethane diamines such as 3.3"-diaminodiphenylmethane, 4,4°-diaminodiphenylmethane, 3.3"-dimethyl-4,4°-diaminodiphenylmethane, 2 .2'-
Bisphenylpropane-based diane such as bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)broban, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfoxide Diphenyl sulfoxide type diamines such as 4,4′-diaξnodiphenylsulfone, diphenylsulfone type cyamines such as 3,3゛-diapolinodiphenylsulfone, benzidine, 3.3゜-dimethylbenzidine, 3.3゜-dimethoxybenzidine, biphenyl-based diaphragms such as 3,3'-diatonobiphenyl, 2,6-diaxinobiridine, 2
．． 5-dia also includes pyridine-based diabenzenes such as nobilidine and 3,4-diaminobiridine, benzene-based diabenzenes such as o-, m-, or p-dianobenzene, and other 4,4-di(
p-Azunophenoxy) diphenylpropane, 4.4'
-di(m-aminophenylsulfonyl)diphenyl ether, 4,4'-di(p-aminophenylsulfonyl)
Diphenyl ether, 4.4゜-di(m-aminophenylthioether) diphenyl sulfide, 4,4゛-di(p-aminophenylthioether) diphenyl sulfide, 4.4゛-di(m-aminophenoxy) diphenyl ketone , 4.4'-di(p-aminophenoxy)diphenylketone, 4.4'-di(m-aminophenoxy)
Diphenylmethane, 4.4°-di(p-aminofuyunoxy)diphenylmethane, 2,5-diaminotoluene, 2
．． 4-diaminoxylene, diaizumi nodulene, 1,5-
Diaminonaphthalene, 2,6-diapolinonaphthalene, etc. are mentioned.

The positive type photosensitive solid millet composition of the present invention contains repeating units having the above structure, and has the general formula [
-OR in [I] and R in 31 are hydrogen atoms or nyloxy groups in a proportion of 5 mol % or more. The proportion of 0-naphthoquinonediazide sulfonyloxy groups should be 5 mol% or more, preferably 5 to 50% by weight. If the content is less than 5 mol%, the polymer itself will have poor photosensitivity, resulting in a high-resolution relief. It becomes difficult to obtain images.

The positive-working photosensitive polyimide composition of the present invention can be obtained, for example, by the following method. First, an aromatic tetracarboxylic dianhydride having the above structure in the molecule and an aromatic diamine containing a hydroxyl group or a mixture of the diamine and another aromatic diamine are mixed in approximately equal moles to any desired amount. The reaction is carried out in an organic solvent using a dehydration condensation agent. Examples of organic solvents include N-methyl-
Examples thereof include 2-pyrrolidone, dimethylacetate, dimethylformamide, dimethylsulfoxide, hexamethylenephosphortriamide, pyridine, pyridinebersol, cresol, phenol, and xylenol. In some cases, a general-purpose solvent such as hexane, benzene, toluene, xylene, alcohol, etc. may be used in combination with the above solvent. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, thionyl chloride, diphenyl chloride phosphate 5, phenylsulfonic acid dichloride, allylsulfonyl chloride, and the like. In addition, in some cases, pyridine, triethylamone, α-
Aromatic or aliphatic tertiary amines such as vicoline, β-vicoline, and T-picoline may be used in combination. The hydroxyl groups in the polyimide precursor assembly thus obtained are 0-naphthoquinonediazide sulfonyloxygenated with 0-naphthoquinonediazide sulfonyl chloride and a tertiary amine to obtain a polyimide precursor assembly. . In addition, it goes without saying that a precursor composite can be similarly obtained by reacting an aromatic diamine component into which a 0-naphthoquinonediazide sulfonyloxy group has been introduced in advance with an aromatic tetracarboxylic dianhydride. .

The solid ξ-doped precursor assembly obtained as described above is
The photosensitive polyide composite of the present invention is obtained by carrying out the ξ-d conversion using a conventional heating method or chemical hydration using acetic anhydride and pyridine.

Since the polyimide composition of the present invention has a polymer skeleton designed to have a specific structure as described above, it has extremely good solubility in organic solvents, such as T-butyrolactone,
It can be dissolved in general-purpose organic solvents such as diglyme, triglyme, cyclohexanone, dioxane, methyl cellosolve, ethyl cellosolve, and chloroform.

The positive type photosensitive polyimide composition of the present invention contains the photosensitive polyimide of the above general formula [I],
A photodegradable proton generator is blended and used. Known substances can be used as such photodegradable proton generators, such as diallylsulfonium salt (Arzl"
X − ), triallylsulfonium salt (ArzS+χ
-), dialkylphenacylsulfonium salts, allyldiazonium salts (^rN," Alternatively, two or more types of proton generators are used in combination.These proton generators are blended in an amount of 1 to 50% by weight, preferably 5 to 15% by weight, based on the aforementioned Bolisendo.When the amount blended is small, acid hydration is used. The decomposition rate slows down, resulting in a decrease in sensitivity, and if the amount is large, it is unfavorable for the stability of the photosensitive solution itself.

An example of a method of forming an image using the positive type photosensitive solid body ξ-domain assembly or proboscis of the present invention will be shown below.

First, a photodegradable proton generator is added to the polyamide,
A photosensitive solution is prepared by dissolving it in an organic solvent and applied onto a substrate. Next, after drying the formed coating film, it is exposed to light through an ordinary photomask.

After exposure, development is performed using a dipping method, a spray method, or the like to remove the irradiated area. The developer used in this case is
It is best to use a solution that can completely dissolve and remove the exposed film within a suitable amount of time, such as an aqueous inorganic alkali solution such as sodium hydroxide or potassium hydroxide, or probylamine, butylamine, monoethanolamine, trimethylammonium hydride, ethylenediamine, trimethylene. Organic diamine compounds such as diamines are used alone or in combination of two or more. In some cases, these amine compounds may be mixed with a poor solvent for the polyide, such as methanol, ethanol, probanol, ethylene glycol, ethyl cellosolve, butyl cellosolve, diethylene glycol, ethyl carbitol, butyl carbitol, water, or the like.

After development, a desired polyimide pattern (image) can be obtained by washing with a rinsing solution. As the rinsing liquid, one or more of methanol, ethanol, water, isoamyl acetate, etc. can be used. Further, a negative pattern can be formed by using an organic solvent such as chloroform or methylene chloride as a developer.

Effects of the Invention The positive type photosensitive polyimide composition of the present invention has a specific structure in which an O-naphthoquinonediazide sulfonyloxy group, which is a photosensitive group, is introduced into the main chain.
- The naphthoquinonediazide sulfonyloxy group is hydrolyzed and becomes alkali-soluble. As a result, it becomes possible to form fine patterns that could not be achieved with conventional positive-type photosensitive polyimide compositions.

Furthermore, since it is solvent soluble, there is no need for high-temperature heat treatment in the imidization process, and relief images with excellent dimensional stability and little volume shrinkage can be obtained. Also, general formula [I]
It is also possible to obtain a negative relief image by controlling the proportion of O-naphthoquinonediazide sulfonyloxy groups therein.

Therefore, the polyimide composition of the present invention can be suitably used as a heat-resistant material or photoresist for forming protective films, insulating films, and passivation films for solid-state devices in the semiconductor industry. .

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

Examples 1 to 3 and Comparative Examples 1 to 2 AR+. in the general formula (1). Aromatic tetracarboxylic dianhydride and aromatic diamine in which ARz and R are the residues in Table 1 are reacted in approximately equimolar amounts in NMP at 25°C to form a polyimide precursor. Obtained. Next, the temperature of this solution was raised to 190'C over 2 hours, and the mixture was further stirred for 6 hours to obtain a polyide solution.

While maintaining this solution at 0°C, predetermined amounts of 0-naphthoquinonediazide sulfonyl chloride and triethyl chloride were added, and the reaction was allowed to proceed at room temperature for 2 hours. A polyide ξ-do containing a quinonediazide sulfonyloxy group was obtained.

The obtained solid ξ-d was mixed into diglyme with a solid concentration of 30
A photosensitive solution was prepared by dissolving the solution in an amount of % by weight. This solution was spin-coated onto a silicone wafer to a dry thickness of 3 μm, and vacuum contact exposure was performed for 3 minutes from a position 30 cm from the light source using a 250 W ultra-high pressure mercury lamp through a quartz mask.

Development was carried out by dipping for 90 seconds using trimethylammonium hydride, followed by dipping for 20 seconds using water as a rinse agent and drying.

When the relief images obtained in this manner were observed using an electron microscope, the aspect ratio of each example product was 1. It was able to resolve the 0 3 μm line. Further, when this relief image was heat-treated at 350''C for 30 minutes, the volumetric shrinkage rate was 10% or less.

In addition, in Example 3, a negative relief image was obtained, and even when the exposure time was varied in the range of 1 to 60 minutes, similar relief images were obtained, and the volume shrinkage rate was 20 to 25%. On the other hand, in Comparative Example 1, the content of 0-naphthoquinonediazide sulfonyloxy group was small, so the exposure time was 30 minutes.
Although the development time was set to 60 minutes or more, the relief image was eroded due to the long immersion, and a good relief image could not be obtained. In addition, in Comparative Example 2, the exposure time was 6
Even if the time was 0 minutes or more, the polyimide only swelled during development and no relief image could be obtained.

(Hereafter, margin)

Claims (1)

[Claims] (1) The following general formula [I], ▲Mathematical formulas, chemical formulas, tables, etc.▼...[I] (However, in the formula, Ar_1 is a tetravalent aromatic hydrocarbon residue, A
r_2 is at least one ortho or meta position of the aromatic ring
is a divalent aromatic hydrocarbon residue having an o-naphthoquinonediazide sulfonyloxy group at two positions), and R is a hydrogen atom or ▲ formula,
A positive photosensitive polyimide composition having a chemical formula, table, etc. ▼, and characterized in that the proportion of the latter is 5 mol% or more.