JPS62117331A - Etching method for aromatic polyether amide resin - Google Patents

Abstract

PURPOSE:To wet-etch of aromatic polyether amide by using a photo-resist employing a specific amide group copolymer as a main agent. CONSTITUTION:A solution of aromatic polyether amide is applied onto a substrate 1 and dried, thus forming a film 2 consisting of the aromatic polyether amide. A composition containing a copolymer of acrylamide and diacetone acrylamide and a sensitizer is applied onto the film 2, thus shaping a photo-resist film 3. Desired sections in the film 3 are irradiated by ultraviolet rays and irradiating sections are cured, and a pattern 4 is formed through development. The exposed film 2 is etched by a solvent (such as N-methyl-2-pyrolidone) dissolving the film 2, and the pattern 4 is peeled. According to said method, the pattern of aromatic polyether amide can be shaped through wet etching.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for etching aromatic polyetheramide resins. More specifically, a photosensitive photoresist film made of a copolymer of acrylamide and diacetone acrylamide with a photosensitizer added thereto is coated on the aromatic polyetheramide resin film.1-1 Desired portions of the resist film are irradiated with ultraviolet rays. 17, draw the pattern, and then perform development process 1-
After forming a desired resist pattern [7], the exposed aromatic polyetheramide resin portion is selectively wet-etched using a polar solvent using the mosquito resist pattern as a mask.

(Conventional technology) Conventionally, aromatic polyetheramide resin has a strength of 9.

Excellent heat resistance, abrasion resistance, solvent resistance, transparency, etc.

Since it dissolves in certain organic solvents, it can be made into a varnish, and has been used for applications such as passivation of semiconductors and protective films for display elements. by the way.

Some of the above applications require electrode extraction parts (through holes) and protective film patterns for hybrid ICICCDs, and for this purpose, it has become necessary to etch the aromatic polyetheramide resin. . There are two etching methods: dry etching using gas and wet etching using etching liquid.

The former is, for example, a method in which polymers are oxidized and decomposed in an oxygen plasma atmosphere for etching. In this case, if a polymer film such as a general-purpose photoresist is used as an etching mask, it will be etched in the same way, so another metal material must be used as the etching mask, which increases the number of steps, which is undesirable. On the other hand, the method using an etching solution allows the use of a general-purpose photoresist and is suitable for mass production processes.

(Problems to be Solved by the Invention) However, when trying to wet-etch an aromatic polyetheramide resin, a general-purpose photoresist cannot be used because of the first problem. In other words, 1. With commonly used positive resists, such as condensates of novolak resin and naphthoquinone (1,2) diazide, when etching aromatic polyetheramide resin with polar solvents, the resists cannot withstand polar solvents. Can not. Aromatic polyetheramide resins have excellent solvent resistance and are not soluble in ordinary organic solvents, but only in some polar solvents with a boiling point of 150° C. or higher. Therefore, the aromatic polyetheramide resin cannot be etched using a general-purpose organic solvent that the resist can withstand. On the other hand, negative resists used for etching polyimide resins, etc.
For example, in the case of a reaction cured product of cyclized rubber and bisazide, the underlying aromatic polyetheramide resin cannot withstand the release liquid 1, such as heated metacresol, when the resist is peeled off. In view of the above, the present invention is an attempt to develop a wet etching method suitable for aromatic polyetheramide resins.

(Means for Solving the Problems) The present invention irradiates a desired portion of a photoresist film formed on a resin film with ultraviolet rays to cure the irradiated portion, and then develops the photoresist film to form a photosensitive photoresist film. In the method of removing the uncured portion of the resist film and then wet-etching the sprayed resin film portion with an etching solution, the resin is an aromatic polyetheramide resin, and the main ingredient of the photoresist film is a mixture of acrylamide and diacetone acrylamide. The present invention relates to a method I for etching aromatic polyetheramide resin, characterized in that the copolymer and the etching solution are polar solvents that dissolve the aromatic polyetheramide resin.

The aromatic polyetheramide resin used in the present invention is a resin in which aromatic groups are bonded via ether bonds and amide bonds, and it is possible to use a resin having repeating units represented by the general formula (Tl). can.

The aromatic polyetheramide resin may have a repeating unit represented by the general formula IUI.

However, in general formulas (I) and (II), a Rt
+ Rll tR3 and R4 represent hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine, and these may be the same or different from each other, R5 and R6 represent hydrogen, methyl group, ethyl group, propyl group , represents a trifluoromethyl group or a trichloromethyl group.

These may be the same or different.
Ar and Ar' are a P-phenylene group, a 2M-phenylene group, a diphenylene group, a naphthylene group, or a (where Y is a bond -〇-, 80!, -C.

Hs -8-, -〇-, -CH*-), which indicates H
s and the like may be the same or different, and X represents an aliphatic group having 2 to 10 carbon atoms which may contain an ether bond or a group similar to Ar'.

Joki aromatic polyetheramide resin has a reduced viscosity of 0.
4-4df/9 (0.2-t thiformaldehyde solution,
30℃) is preferable. If the reduced viscosity is too low, the heat resistance of the resin tends to decrease.

If it is too large, the solubility in solvents will decrease (2).

The aromatic polyetheramide resin is composed of an aromatic dicarboxylic acid or a reactive derivative thereof and a general formula (1111% formula% (wherein 1 formula, r R1r Rs, ns + R4
+Rs and Ru mean the same thing as in the above general formula (I)) and, if necessary, the general formula +IVI HO-X-OHflV) (however, in the 2nd formula , X, meaning the same as in the case of general formula (I[)), and solution polymerization.

It can be obtained by melt polymerization or condensation polymerization by a known aromatic polyamide manufacturing method such as the method disclosed in JP-A-51-23198.

Here, the compounds represented by the general formula +l1l) and the general formula (1%') have a molar ratio of 515 to 1010 for the former/latter.
It is preferable to mix them so that If this ratio is too small, heat resistance tends to decrease. tfr, this ratio is particularly preferably 9/1 or less in order to improve the adhesiveness of the resin.

In addition, based on the total amount of the compound represented by the general formula (I'll) and the compound represented by the general formula (IVI) used as necessary, the aromatic dicarboxylic acid or its reactive acid derivative is Preference is given to using molti, particularly preferably 100 molti or approximately 100 molti.

The aromatic diamine having an ether bond represented by the general formula (1111) is 2.2-bisC4-(4-
aminophenoxy)phenyl]propane, 2.2-bis[3-methyl-4-(4-aminophenoxy)phenyl]furopane, 2.2-bis[:3-7'romo4-
(4-aminophenoxy)phenyl]furopane, 2.2
-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-propyl-4-
(4-aminophenoxy)phenyl]propane, starbis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-butyl-4
-(4-aminophenoxy]phenyl]propane, 2.
2-bis(3-5ec-butyl-4-(4-aminophenoxy)phenyl)propane, 2,2-bis[3-methoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[ 3-Ethoxy-4-(4-aminophenoxy)phenyl]propane.

2.2-bis[tortoise 5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 212-bis[3,5-
Dichloro-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-cyfuromo-4-(
4-aminophenoxy)phenyl]propane, 2.2-
Bis[&5-dimethoxy4-(4-aminophenoxy)phenyl]propane.

λ2-bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]propane, i,i-bis(4
-(4-aminophenoxy)phenyl]ethane, 1.1
-bis[3-methyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4
-aminophenoxy)phenyl]ethane, 1.1-bis[3-bromo-4-(4-aminophenoxy)phenyl]ethane, 1゜1-bis[3-ethyl-4-(4-aminophenoxy)phenyl] Ethane, 1.1-bis[3-
Propyl-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 1゜1-bis[3
-butyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(3-see-butyl-4-(4-
aminophenoxy)phenyl]ethane, 1,1-bis[
3-Methoxy-4-(4-aminophenoxy)phenyl]ethane, 1゜1-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(3,
5-dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dichloro-4-(4
-aminophenoxy)phenyl]ethane, 1. l-bis(3,5-dibromo-4-(4-aminophenoxy)phenyl)ethane, 1,1-bis[3,5-dimethoxy-
4-(4-aminophenoxy)phenyl]ethane, 1,
1-bis[3-chloro-4-(4-aminophenoxy)
-5-methylphenyl]ethane, bisC4-(4-aminophenoxy)phenylcomethane, bis[3-methyl-
4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-4-(4-aminophenoxy)phenylcomethane, bis[3-bromo-4-(4-aminophenoxy)phenylcomethane, bis[ 3-ethyl-4-(4
-aminophenoxy)phenylcomethane, bis[3-propyl-4-(4-aminophenoxy)phenylcomethane, bis[3-isopropyl-4-(4-aminophenoxy]phenyl]methane, bis[3-butyl- 4-(4
-aminophenoxy)phenylcomethane, bis(3-s
ee --7'thyl-4-(4-aminophenoxy)phenylcomethane, bis[3-methoxy-1-(4-aminophenoxy)phenol]methane, bis[3-nitoxy-4-(1-amino phenoxy) phenylcomethane, bis[3,5-dimethyl-4-(4-aminof J. Nogishi)]
Noenyl]methane, bis[3゜5-dichloro-4-(4
-aminophenoxy]phenyl]methane, bis[3,5
-dibromo-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dimethoxy-4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-
4-(4-aminophenoxy)-5-methylphenylcomethane, 1,1,1,3.3,3-hexafluoro-4
2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3.3-hegizachloro42-bisC4-(4-aminophenoxy)phenyl]
Propane, 3.3-bis(4-(4-aminophenoxy)phenyl)pentane, 1.1-bis[4-(4-aminophenoxy)phenyl]propane.

1, 1.1.3.3.3--Hex Fluoro 2.2-
Bis[3゜5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.3.3-
Bekizachloro2,2-bis[3,5-dimethyl-4-
(4-aminophenoxy)phenyl]propane, 3.3
-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]pentane, 1.1-his[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1.1.1 .3.3.3-hexafluoro-2
, 2-bis[3,5-dibromo-4(4-aminophenoxy)phenyl]propane, 1,1,1,3,3.
3-hexachloro-2,2-bis[3+5-dibromo-
4-(4-aminophenoxy)phenyl]propane, 3
．． 3-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,5-
dibromo-4-(4-aminophenoxy)phenyl]propane, 2-bisC4-(4-aminophenoxy)phenyl]butane'', λ2-bis[3-methyl-4-(4
-aminophenoxy)phenylcobutane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenylcobutane, 2゜2-bis[λ5-dibromo4-
(4-amitsuquenoxy)phenylcobutane, 1,
Examples include 1,1,3,3.3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane. Among them, 2,2-bis[4=-(4-'7" minophenyl]phenyl]propane is representative. If desired, mixtures of the above diamines can be used.

Furthermore, known diamines such as 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
4.4'-diaminodiphenylsulfone, metaphenylenediamine, 4.4'-di(4-aminophenoxy)phenylsulfone, paraphenylenediamine, 4.4'-
Di(3-aminophenoxy)phenyl sulfone, 3.3
15. Combined use of at least one type of '-diaminodiphenylsulfone etc. If you use it, you can make a. The ratio of these diamines to the total diamines is desirably 80 molti or less. If this ratio exceeds 80 molar ratio, it will adversely affect the solubility of the dipolymer, which is preferable. Especially desirable is 30 molti or less.

Representative examples of compounds represented by the general formula flV) include:

Bisphenol A may be mentioned.

By copolymerizing the compound represented by the general formula (■), it is possible to improve the adhesion to a substrate (particularly a polyethylene terephthalate film).

Aromatic dicarboxylic acid in the present invention and [7.

For example, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid-4,4'e diphenylsulfonedicarboxylic acid-4,4', -diphenyldicarboxylic acid-4,4'
', and hinaphthalene dicarboxylic acid-1,5%Q, but terephthalic acid and isophthalic acid are commonly produced and can be preferably used. In particular, a mixture of terephthalic acid and isophthalic acid is desirable from the viewpoint of solubility of the resulting polymer. In addition, the reactive acid derivative of aromatic dicarboxylic acid in the present invention means dichloride, dipromide, diester, etc. of aromatic dicarboxylic acid.

In the present invention, when a mixture of terephthalic acid and isophthalic acid is used, the blending ratio of isophthalic acid having a carboxyl group at the meta position of the benzene nucleus and terephthalic acid having a carboxyl group at the distal position of the benzene nucleus is the former 2.
It is desirable that the latter range from 0 to 80% to 80 to 20%, especially from the viewpoint of solubility in organic solvents.

The above aromatic polyether amide polymer is dissolved in a polar solvent.

The polar solvent and 12 are acetamide, N,N-dimethylformamide, and N,N-dimethylacetamide.

Examples include N,N-diethylformamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitrobenzene, di-11 alcohol carbonate, cyclohexanone, etc. These can be used alone or in combination of two types. used.

An aromatic polyetheramide resin is deposited on a substrate that requires etching. Examples of substrates include glass or polyethylene terephthalate films on which transparent electrodes such as indium oxide used for liquid crystal display devices are formed, ceramics used as substrates for semiconductor devices, glass epoxy, and the like.

There are silicon plates, aluminum plates, silicon wafers, etc. that have silicon oxide films.

Film formation can be carried out by applying a varnish prepared by dissolving an aromatic polyetheramide resin in the above-mentioned polar solvent onto a substrate and drying it. The resin concentration of the varnish is not particularly limited, and is preferably 1 to 35% by weight. The drying temperature is
For example, 18 at 100°C, depending on the case.
It may be 0°C.

The film thickness is appropriately determined depending on the application and is usually in the range of 500 angstroms to 300 μm.

The photoresist film contains a copolymer of acrylamide and diacetone acrylamide as a main ingredient, and further contains a photosensitizer for ultraviolet rays.

The copolymer of acrylamide and diacetone acrylamide in the present invention is obtained by copolymerizing acrylamide, diacetone acrylamide, and, if necessary, other polymerizable polymers. In the copolymer, acrylamide/
-) Acetone acrylamide in a molar ratio of 1.5/1
~2.2/1 is preferred.

If the amount of acrylamide is too low, the sensitivity during ultraviolet irradiation tends to be low (the curing reaction of the irradiated area becomes insufficient); on the other hand, if it is too high, the resist in the cured area tends to be easily attacked by polar solvents.

The molar ratio of acrylamide/diacetone acrylamide is preferably 1.7/1 to 2.0/1.

The other monomer monomer mentioned above is acrylic acid.

Methacrylic acid, hydroxyethyl methacrylate.

There are hydroxyethyl acrylate, methyl methacrylate, styrene, sulfonated styrene, etc., and these are preferably used in the L copolymer in an amount of 5% by weight or less.

The -U-pi copolymer can be obtained by copolymerizing a predetermined amount of the above monomer in water. In the case of 1, radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile, potassium persulfate, redox initiators, etc. can be used as the polymerization initiator.

As the Akane photosensitizer, sodium 4,4'-diazidostilbene-2,2'-disulfonate, 1,5-sia 1
Sodium 8-1-cyto-naphthalene-3,7-disulfonate,
There are azide compounds such as 4.4'-diazide-benzophenone, 4.4''-diazide-diphenylmethane, 4.4'-diazide-stilbene, etc.
It is preferable to use ~40 pieces.

Particularly preferred is VC10-20 polydisperse. If the amount of the photosensitizer is too small, the crosslinking reaction between the copolymers will be insufficient during ultraviolet irradiation, and if it is too large, the crosslinking reaction will tend to be non-uniform.

To form a photoresist film, the copolymer and photosensitizer are dissolved in water to form a photoresist composition, and this is applied onto the aromatic polyneedleamide resin film by spinner coating, screen printing, offset printing, etc. It can be applied by applying and drying with air or hot air.

The photoresist composition has a temperature of 200 to 1000 at 25°C.
It is preferable to adjust it so that it becomes cp. If the viscosity is too low, the film will be too thin, and if the viscosity is too high, it will be difficult to apply. The photoresist film preferably has a thickness of 2,000 angstroms to 2 μm. If it is too thin, it will not be possible to retain the aromatic polyetheramide resin film that should remain sufficiently during etching, and if it is too thick, it will be difficult to completely cure the irradiated area when irradiated with ultraviolet rays.

Desired portions of a photoresist film are irradiated with ultraviolet rays, and for this purpose, there is a method of placing a mask pattern on the film and irradiating this with ultraviolet rays. A general-purpose ultra-high pressure mercury lamp can be used for the ultraviolet irradiation, and the irradiation amount is preferably 40 to 60 m, T/cm'.

After UV irradiation, a photoresist is formed by development. The development treatment can be carried out by washing the photoresist film irradiated with ultraviolet light with warm water at 40 to 80° C. and dissolving the non-irradiated portions. The cleaning method includes a shower method, immersing the film in warm water, and 2. There are ways to shake it out.

After the photoresist is formed on the aromatic polyetheramide resin film as described above, the sprayed portion of the resin film is etched with an etching solution. As the etching solution, the above-mentioned polar solvent can be used, and as an etching method.

There are methods such as showering the polar solvent onto the aromatic polyetheramide resin film, and immersing the resin film in the polar solvent and shaking it off.

After etching, the photoresist is etched by a method such as spraying a diluted aqueous solution in which hydrogen peroxide and sulfamic acid secondary hypochlorite sorter are dissolved, or immersing the photoresist in the diluted aqueous solution and shaking it. The resist can be peeled off.

Here, the concentration of hydrogen peroxide ij: 0.2 to 5 times,
What is the concentration of sulfamic acid, sodium hypochlorite, etc.?

0.02 to 0.5 fold is preferable. If these concentrations are too small, the photoresist will not be peeled off sufficiently, and if it is too large, the substrate or wiring formed on the substrate will be easily attacked.

In the present invention, when etching the aromatic polyetheramide resin, a copolymer of acrylamide and diacetone acrylamide is used as the main ingredient of the photoresist film.

The liquid used for developing photoresist films, etching aromatic polyetheramide resins, and peeling off photoresists can effectively dissolve or peel off only the desired components. Resin can be etched.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are illustrative and do not limit the scope of the present invention.

Embodiment FIG. 1 is a schematic cross-sectional structural diagram of an etching process carried out according to the present invention. (A) 20% by weight on glass substrate
This figure shows a state in which an N-methyl-2-pyrrolidone solution of the aromatic polyetheramide resin is applied. After applying the aromatic polyetheramide resin with a spinner at 1.50 Or, p, m.

It was dried at 150° C. for 2 hours, and the film thickness was adjusted to 4 μm by 1°.

(81 shows the state in which a photoresist composition is applied on an aromatic polyetheramide resin film to form a photoresist film. As a photoresist composition, an acrylamide-diacetone acrylamide copolymer (acrylamide: Diacetone acrylamide-1,8:1;
4.4'-Diazidostilbene-42'-disulfonic acid sodium salt was added to a 4-fold aqueous solution of the same molar ratio (mole ratio) in a 20-layer ratio to the resin. Coating was carried out using all spinners at 2.00 Or, p, m, and drying was carried out in dry air at 50° C. for 5 minutes. The film thickness of the photoresist film after drying was adjusted to 1.5 μmVr' and fA. (C1 shows the state after covering -F of the photoresist film with a mask and irradiating ultraviolet rays.
50 tn using a 00W ultra-high pressure mercury lamp (manufactured by Seisaku Denki),
Exposure was made at T/cm''.

(Dl indicates the state after developing the resist composition.

Development was carried out in warm water at 60° C. for 30 seconds. After development, the film was rinsed with running water and dried with dry air at 50°C for 5 minutes. (E) shows the state after etching the aromatic polyetheramide resin film. Use N-methyl-2-pyrrolidone in the etching solution.

Etching was performed for 30 seconds at room temperature. After etching, it was cleaned with isopropanol.

fF) removes the resist #1. Shows the state after The remover is 0.5 weight hydrogen peroxide! 91 = and sulfamic acid 0.
The film was peeled off at 60° C. for 1 minute using a 0.5% by weight aqueous solution.

In addition, for the upper rudder, aromatic polyetheramide resin and those obtained by the following two manufacturing methods 1 to 1 were used separately. The results were similar in both cases.

(1) 10100O! into the flask, a stirring stick,
Set a dropping funnel with two thermometers, dissolve 17.2 g of NaOH in 80 ml of water, and pour into the flask. Next, 2゜2
44.39 g of bis(4(4-aminophenoxy)phenyl)propane and 16.49 g of bisphenol A were dissolved in 340 g of cyclohexanone, poured into a two-point flask, and cooled to -2°C.Meanwhile, terephthalic acid dichloride 18.29 and isophthalic acid dichloride is, 2
g was dissolved in cyclohexanone 2409, and this acid chloride solution was injected into the flask from the dropping funnel, and the two reactions were allowed to react for 3 hours so that the temperature did not exceed 10°C.

The reaction solution was poured into methanol to isolate the polymer.

After drying this, it was dissolved again in dimethylformamide and poured into methanol to purify the aromatic polyether ester amide condensation polymer (9).

Reduced viscosity (vsp/c) of this polymer (0.2% by weight solution of dimethylformamide, measured at 30°C, same hereinafter), 9 dI! /g.

(2) A varnish was prepared in the same manner as in (1) above, except that raw materials with a uniform composition were used.

The reduced viscosity (ηsp/e) of this polymer is 1.3 dl/
It was 9.

(Effects of the Invention) The present invention enables a wet etching method for aromatic polyetheramide resin, making it possible to apply the resin to semiconductor devices and other electronic components that require through holes and patterns. Became.

In addition, 2) the etching method of the present invention can use an organic solvent for the etching solution, and can use hot water for the development process; ing.

[Brief explanation of drawings]

Figure 1 shows the etching T of aromatic polyetheramide resin.
It is a cross-sectional schematic diagram showing the process step by step. Explanation of symbols 1...Glass substrate

Claims (1)

[Claims] 1. After irradiating the desired part of the photoresist film formed on the resin film with ultraviolet rays and curing the irradiated part, development is performed to form a photoresist, and then the exposed resin film part is exposed to an etching solution. In the wet etching method, the resin is an aromatic polyetheramide resin, the main ingredient of the photoresist film is a copolymer of acrylamide and diacetone acrylamide, and the etching solution dissolves the aromatic polyetheramide resin. A method for etching aromatic polyetheramide resin, which is characterized by using a polar solvent.