JPH07258370A - Production of polyurea film - Google Patents

Abstract

PURPOSE:To provide a method for producing by vapor deposition polymn., a polyurea film which does not undergo thermal decomposition even when heated to 230-300 deg.C. CONSTITUTION:A diamine component and a diisocyanate component are evaporated separately from different evaporation sources and are subjected to vapor deposition polymn. to form a polyurea film on the surface of a substrate plate. The film is then irradiated with UV rays and/or electron beams.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a polyurea film, and more particularly to a method for producing a polyurea film for resist or electrical insulation.

[0002]

2. Description of the Prior Art Polyurea obtained by vapor deposition polymerization is 230
When heated to ~ 300 ° C, thermal decomposition occurs. For example, when a thin film polyurea is heated to 230 to 300 ° C., the thin film has a property of thermally decomposing and disappearing.

[0003]

The object of the present invention is 23
Another object of the present invention is to provide a method for producing a polyurea thin film by vapor deposition polymerization that does not cause thermal decomposition even when heated to 0 to 300 ° C.

[0004]

The first aspect of the present invention is to evaporate (a) a diamine component and (b) a diisocyanate component from different evaporation sources in a vacuum, and vaporize and polymerize the same on a substrate surface. To a polyurea film, and then irradiating the polyurea film with an ultraviolet ray and / or an electron beam. The second aspect of the present invention is to evaporate (a) a diamine component, (b) a diisocyanate component and (c) a sensitizer from different evaporation sources in a vacuum, and deposit the polyurea on a substrate surface by vapor deposition polymerization. The present invention relates to a method for producing a polyurea film, which comprises forming a film and then irradiating the polyurea film with an ultraviolet ray and / or an electron beam. A third aspect of the present invention is to evaporate (a) a diamine component and (b) a diisocyanate component from different evaporation sources in a vacuum, and form a polyurea film on the surface of the substrate by vapor deposition polymerization. , (C) a sensitizer is vapor-deposited on the polyurea film from another evaporation source, which is repeated if necessary, and then this is irradiated with an ultraviolet ray and / or an electron beam. The present invention relates to a method for manufacturing a membrane.

The method for producing a polyurea film of the present invention is useful as a pattern forming method and a pattern forming method using a polyurea film. The specific method is as follows. That is, a raw material monomer of polyurea is evaporated in a vacuum, and a polyurea film is formed by vapor deposition polymerization on the surface of a substrate. Then, the formed polyurea film is exposed to ultraviolet rays and / or UV light using a photomask for pattern formation. After irradiating with an electron beam and exposing, the polyurea film is heated to thermally decompose and remove the film in the unexposed portion to form a pattern on the polyurea film.

This pattern forming method is extremely useful as a pattern forming method for electronic circuits and the like, and by carrying out these steps in a vacuum, it is possible to prevent contamination of impurities and dust during the pattern forming process. However, there are many advantages such as the lack of the steps of treatment with a developing solution and its washing as in the conventional method.

In carrying out this method, if a coloring agent is used as another evaporation source, the polyurea film can be colored simultaneously with the formation of the patterned polyurea film, and a pattern is formed on the substrate. It can also be used as a method of doing.

Examples of the (a) diamine component which can be used in the present invention include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and 4,4 '.
-Diamino-3,3'-dimethyldiphenylmethane,
3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5
5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 4,4'
-Methylene-bis (2-chloroaniline), 4,4'-
Diaminodiphenyl sulfone, 2,7-diaminofluorene, 4,4'-diamino-p-terphenyl, 1,3
One kind or a mixture of two or more kinds such as -diamino-5-cyanobenzene can be used.

Examples of the (b) diisocyanate component that can be used in the present invention include methylenediphenyl 4,4'-diisocyanate and 3,3'-dimethyldiphenyl-
4,4'-diisocyanate, o-dianisidine diisocyanate, methylenebis (4-isocyanate-3-
Methylbenzene), methylenebis (4-isocyanato-2-methylbenzene), methylenebis (o-chlorophenylisocyanate), 5-chloro-2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI). ), 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 3,5-diisocyanate benzotrifluoride, bis (4-isocyanate) Natophenyl) ether, dicyclohexylmethane-4,
4'-diisocyanate, norbornane diisocyanate methyl, p-phenylene diisocyanate, p-xylene diisocyanate, tetramethyl xylene diisocyanate, 1,5-naphthalene diisocyanate, 2,
6-naphthalene diisocyanate, trans-1,4-
Cyclohexyl diisocyanate, isophorone diisocyanate 1,3-bis (isocyanatomethyl) benzene, etc. may be used alone or in combination of two or more.

Preferred polyureas include the following a / b
The polyurea obtained by the combination of 4,
4'-diaminodiphenylmethane / 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4'-
Diaminodiphenylmethane / o-dianisidine diisocyanate, 4,4'-diaminodiphenylmethane / methylenebis (4-isocyanato-2-methylbenzene), 4,4'-diaminodiphenylmethane / 4,4 '
-Diphenylmethane diisocyanate (MDI), 4,
4'-diaminodiphenylmethane / 2,4-toluene diisocyanate (2,4-TDI), 4,4'-diaminodiphenylmethane / 2,6-toluene diisocyanate (2,6-TDI), 4,4 ' -Diaminodiphenylmethane / bis (4-isocyanatophenyl) ether, 4,4'-diaminodiphenylmethane / p-phenylene diisocyanate, 4,4'-diaminodiphenylmethane / 1,5-naphthalene diisocyanate, 4,
4'-diaminodiphenyl ether / 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4 '
-Diaminodiphenyl ether / o-dianisidine diisocyanate, 4,4'-diaminodiphenyl ether / methylenebis (4-isocyanato-2-methylbenzene), 4,4'-diaminodiphenyl ether / 4,
4'-diphenylmethane diisocyanate (MDI),
4,4'-diaminodiphenyl ether / 2,4-toluene diisocyanate (2,4-TDI), 4,4'-
Diaminodiphenyl ether / 2,6-toluene diisocyanate (2,6-TDI), 4,4′-diaminodiphenyl ether / bis (4-isocyanatophenyl) ether, 4,4′-diaminodiphenyl ether / p-phenylenediene Isocyanate, 4,4'-diaminodiphenyl ether / 1,5-naphthalene diisocyanate, 4,4'-diaminodiphenyl ether / 1,
3-bis (isocyanatomethyl) benzene, 4,4 '
-Diamino-3,3'-dimethyldiphenylmethane /
3,3'-Dimethyldiphenyl-4,4'-diisocyanate 4,4'-Diamino-3,3'-dimethyldiphenylmethane / o-dianisidine diisocyanate, 4,
4'-diamino-3,3'-dimethyldiphenylmethane / methylenebis (4-isocyanato-2-methylbenzene), 4,4'-diamino-3,3'-dimethyldiphenylmethane / 4,4'-diphenylmethanediisocyanate (MDI), 4,4'-diamino-3,3'-dimethyldiphenylmethane / 2,4-toluene diisocyanate (2,4-TDI), 4,4'-diamino-3,
3'-Dimethyldiphenylmethane / 2,6-toluene diisocyanate (2,6-TDI), 4,4'-diamino-3,3'-dimethyldiphenylmethane / bis (4-)
Isocyanatophenyl) ether, 4,4'-diamino-3,3'-dimethyldiphenylmethane / p-phenylene diisocyanate, 4,4'-diamino-3,3 '
-Dimethyldiphenylmethane / 1,5-naphthalene diisocyanate, 3,3'-dimethoxy-4,4'-diaminobiphenyl / 3,3'-dimethyldiphenyl-4,
4'-diisocyanate, 3,3'-dimethoxy-4,
4'-diaminobiphenyl / o-dianisidine diisocyanate, 3,3'-dimethoxy-4,4'-diaminobiphenyl / methylenebis (4-isocyanate-2-
Methylbenzene), 3,3'-dimethoxy-4,4'-
Diaminobiphenyl / 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethoxy-4,
4'-diaminobiphenyl / 2,4-toluene diisocyanate (2,4-TDI), 3,3'-dimethoxy-
4,4'-diaminobiphenyl / 2,6-toluene diisocyanate (2,6-TDI), 3,3'-dimethoxy-4,4'-diaminobiphenyl / bis (4-isocyanatophenyl) ether, 3,3'-dimethoxy-
4,4'-diaminobiphenyl / p-phenylene diisocyanate, 3,3'-dimethoxy-4,4'-diaminobiphenyl / 1,5-naphthalene diisocyanate,
3,3'-dimethyl-4,4'-diaminobiphenyl /
3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-dimethyl-4,4'-diaminobiphenyl / o-dianisidine diisocyanate, 3,3 '
-Dimethyl-4,4'-diaminobiphenyl / methylenebis (4-isocyanato-2-methylbenzene),
3,3'-dimethyl-4,4'-diaminobiphenyl /
4,4'-diphenylmethane diisocyanate (MD
I), 3,3'-dimethyl-4,4'-diaminobiphenyl / 2,4-toluene diisocyanate (2,4-T
DI), 3,3'-dimethyl-4,4'-diaminobiphenyl / 2,6-toluene diisocyanate (2,6-
TDI), 3,3'-dimethyl-4,4'-diaminobiphenyl / bis (4-isocyanatophenyl) ether, 3,3'-dimethyl-4,4'-diaminobiphenyl / p-phenylene diisocyanate , 3,3'-Dimethyl-4,4'-diaminobiphenyl / 1,5-naphthalene diisocyanate, 4,4'-methylene-bis (2
-Chloroaniline) / 3,3'-dimethyldiphenyl-
4,4'-diisocyanate, 4,4'-methylene-bis (2-chloroaniline) / o-dianisidine diisocyanate, 4,4'-methylene-bis (2-chloroaniline) / methylenebis (4 -Isocyanato-2-methylbenzene), 4,4'-methylene-bis (2-chloroaniline) / 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-methylene-bis (2-chloro) Aniline) / 2,4-toluene diisocyanate (2,4-TDI), 4,4'-methylene-bis (2-
Chloroaniline) / 2,6-toluene diisocyanate (2,6-TDI), 4,4′-methylene-bis (2-)
Chloroaniline) / bis (4-isocyanatophenyl) ether, 4,4'-methylene-bis (2-chloroaniline) / p-phenylene diisocyanate, 4,
4'-methylene-bis (2-chloroaniline) / 1,5
-Naphthalene diisocyanate, 1,3-diamino-5
-Cyanobenzene / 2,6-naphthalene diisocyanate,

When the polyurea film formed on the substrate is irradiated with ultraviolet rays and / or electron beams, a crosslinking reaction occurs in the polyurea film, and the polyurea portion irradiated with ultraviolet rays and / or electron beams is not depolymerized. Since it becomes polyurea, if heat treatment is performed after irradiation with ultraviolet rays and / or electron beams, polyurea in the unirradiated portion can be evaporated and removed by depolymerization.

In the polyurea film manufacturing process, the sensitizer is evaporated at the same time as the raw material monomer and dispersed in the polyurea thin film layer, or after the polyurea thin film is formed, it is increased from another evaporation source. It is also possible to evaporate the sensitizer and disperse it on the surface of the polyurea film.

The sensitizer contains UV rays and / or
Or, it absorbs an electron beam and is excited to generate a free radical, which accelerates the depolymerization and photocrosslinking reaction of the polyurea in the irradiated area, which shortens the exposure time by improving the sensitivity and improves the patterning processing accuracy. To do.

Usually, the sensitizer is added in an amount of about 0.1 to 10% by weight based on the polyurea thin film.

These sensitizers are classified into self-cleavage type and hydrogen abstraction type. The self-cleavage type is a type that absorbs and excites an ultraviolet ray and / or an electron beam to generate a radical by intramolecular cleavage, and is acetophenone-based, diketone-based,
An acyl oxime ester etc. are mentioned. The hydrogen abstraction type efficiently extracts hydrogen from a raw material monomer or solvent by photoexcitation to generate a radical, and examples thereof include aromatic ketones.

Examples of the sensitizer used in the present invention include the following. 1) Aromatic ketones Benzophenone, xanthone, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone, N,
N, N ', N'-tetraethyl-4,4'-diaminobenzophenone, etc. 2) Acetophenones Acetophenone, trichloroacetophenone, p-N,
N-dimethylaminoacetophenone, 2-hydroxy-
2-methyl-propiophenone, benzoin ether,
2,2'-diethoxyacetophenone etc. 3) Benzoic acids p-N, N-dimethylaminoisoamyl benzoate, p-
Ethyl N, N-dimethylaminobenzoate, etc. 4) Diketones, benzyl, methylbenzoyl formate, etc. 5) Others Acyloxime esters, acylphosphine oxides, etc.

In the vapor deposition polymerization chamber, the degree of vacuum when vaporizing the raw material monomers to vaporize and polymerize on the substrate is as follows.
1.3 × 10 ^{−3 to} 1.3 × 10 ⁻² Pa (1 × 10 ⁻⁵ to 1)
It is set to approximately 10 ⁻⁴ Torr).

As a material of the substrate on which the raw material monomers are vapor-deposited and polymerized, a polyurea film is formed and then irradiated with ultraviolet rays and / or electron beams to form a pattern by heating. As long as the material has a property such as glass, silicon wafer, metal plate,
Examples thereof include a polyimide film.

The degree of vacuum when the polyurea film on the substrate is irradiated with ultraviolet rays and / or electron beams in the exposure chamber is 1.3 × 10 ^{−3 to} 1.3 × 10 ⁻² Pa (1 ×). 10
^-5 to 1 × 10 ^-4 Torr) is set.

The temperature for heating the polyurea film irradiated with ultraviolet rays and / or electron beams in the developing chamber is set depending on the thickness of the polyurea film, the type of the polyurea film, and the material of the substrate. Generally, the temperature is about 250 to 330 ° C,
The degree of vacuum when heating is from 1.3 × 10 ⁻³ to
1.3 × 10 ⁻² Pa (1 × 10 ⁻⁵ to 1 × 10 ⁻⁴ Tor
r) Set to about.

In the pattern forming apparatus used in the embodiment of the present invention, an evaporation source for evaporating a raw material monomer of a photosensitive synthetic resin in a vacuum and a substrate on which a polyurea film is formed by vapor deposition polymerization of the raw material monomer are opposed to each other. Vapor deposition polymerization chamber arranged as
An ultraviolet source and / or an electron beam source for irradiating a polyurea film on a substrate with an ultraviolet ray and / or an electron beam, an exposure chamber in which a photomask for forming a pattern on the polyurea film is arranged, and an ultraviolet ray and / or an electron beam And a developing chamber in which a heating device for performing a heat treatment on the polyurea film after the irradiation and exposure is disposed.

FIG. 1 shows an example of a pattern forming apparatus. A vapor deposition polymerization chamber 1 for forming a polyurea film, an exposure chamber 2 for irradiating the polyurea film with ultraviolet rays, and a polyurea irradiated with ultraviolet rays. The urea film is composed of a developing chamber 3 for heat treatment, and a valve 4 connects the vapor deposition polymerization chamber 1, the exposure chamber 2, and the developing chamber 3 in this order.

A vacuum chamber 7 connected to an external vacuum pump or other vacuum exhaust system 6 via a valve 5 is arranged upstream of the vapor deposition polymerization chamber 1, and a valve 8 is provided downstream of the developing chamber 3. A vacuum chamber 10 connected to an external vacuum pump or other vacuum evacuation system 9 via the vacuum evacuation system 6 is disposed, and either one of the evacuation system 6 and the evacuation system 9 or both evacuation systems are actuated to form a vapor deposition polymerization chamber. The inside of the chamber 1, the inside of the exposure chamber 2 and the inside of the developing chamber 3 can be set to predetermined pressures.

A substrate holder 12 for holding a substrate 11 for forming a vapor deposition polymerization film (polyurea film) is arranged in the vapor deposition polymerization chamber 1, and the substrate holder 12 is opposed to the substrate 11 below the vapor deposition polymerization chamber 1. Diamine as one raw material monomer (a) of the polyurea film, and the other raw material monomer (b)
As the evaporation sources 13 and 13 made of glass for respectively evaporating diisocyanate, the evaporation source 14 for crystal vibration provided in the vicinity of each evaporation source 13 and the heater 15 are used to supply the raw material monomer ( The evaporation amounts of a) and (b) can be controlled at a predetermined temperature that always keeps the amount constant.

Further, a shutter 16 is arranged between the substrate 11 and both evaporation sources 13, and a partition plate 17 is provided between both evaporation sources 13.

A substrate holder 12 is provided below the inside of the exposure chamber 2.
An ultraviolet source 18 is provided so as to face the substrate 11 held by the substrate 11, a photomask 19 having a pattern of a predetermined shape is provided in front of the substrate 11, and the substrate 11 is placed in the vapor deposition polymerization chamber 1.
The polyurea film formed on the surface was irradiated with ultraviolet rays from the ultraviolet source 18 to be exposed in a pattern.

A heating device 20 composed of a halogen lamp is provided on the rear side of the substrate 11 held by the substrate holder 12 in the developing chamber 3, and a polyurea film cross-linked by being irradiated with ultraviolet rays in the exposure chamber 2 is predetermined. The polyurea film in the non-exposed area was depolymerized and removed by heating to a temperature.

The embodiments of the present invention are listed below. (1) In a vacuum, (a) diamine component and (b) diisocyanate component are evaporated from different evaporation sources, and a polyurea film is formed on the surface of a substrate by vapor deposition polymerization, and then this polyurea is formed. A method for producing a polyurea film, which comprises irradiating the film with ultraviolet rays or an electron beam. (2) Evaporating (a) diamine component, (b) diisocyanate component, and (c) sensitizer from different evaporation sources in a vacuum, and forming a polyurea film on the surface of the substrate by vapor deposition polymerization. Then, a method for producing a polyurea film, which comprises irradiating the polyurea film with an ultraviolet ray or an electron beam. (3) In a vacuum, (a) diamine component and (b) diisocyanate component are evaporated from separate evaporation sources to form a polyurea film on the surface of the substrate by vapor deposition polymerization, and then (c) A method for producing a polyurea film, which comprises depositing a sensitizer from different evaporation sources on the polyurea film, repeating the process if necessary, and irradiating the polyurea film with an ultraviolet ray or an electron beam. (4) The method for producing a polyurea film according to (1), (2) or (3) above, wherein the polyurea film is a resist polyurea film. (5) The combination of the diamine component of (a) and the diisocyanate component of (b) is 4,4'-diaminodiphenylmethane / 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4 '. -Diaminodiphenylmethane / o
-Dianisidine diisocyanate, 4,4'-diaminodiphenylmethane / methylenebis (4-isocyanato-2-methylbenzene), 4,4'-diaminodiphenylmethane / 4,4'-diphenylmethane diisocyanate (MDI), 4 , 4'-diaminodiphenylmethane /
2,4-Toluene diisocyanate (2,4-TD
I), 4,4'-diaminodiphenylmethane / 2,6-
Toluene diisocyanate (2,6-TDI), 4,
4'-diaminodiphenylmethane / bis (4-isocyanatophenyl) ether, 4,4'-diaminodiphenylmethane / p-phenylene diisocyanate, 4,
4'-diaminodiphenylmethane / 1,5-naphthalene diisocyanate, 4,4'-diaminodiphenyl ether / 3,3'-dimethyldiphenyl-4,4'-diisocyanate 4,4'-diaminodiphenyl ether /
o-dianisidine diisocyanate, 4,4′-diaminodiphenyl ether / methylenebis (4-isocyanato-2-methylbenzene), 4,4′-diaminodiphenyl ether / 4,4′-diphenylmethane diisocyanate (MDI), 4,4'-diaminodiphenyl ether / 2,4-toluene diisocyanate (2,4-
TDI), 4,4'-diaminodiphenyl ether /
2,6-Toluene diisocyanate (2,6-TD
I), 4,4'-diaminodiphenyl ether / bis (4-isocyanatophenyl) ether, 4,4'-
Diaminodiphenyl ether / p-phenylene diisocyanate, 4,4'-diaminodiphenyl ether /
1,5-naphthalene diisocyanate, 4,4'-diaminodiphenyl ether / 1,3-bis (isocyanatomethyl) benzene, 4,4'-diamino-3,3'-
Dimethyldiphenylmethane / 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4'-diamino-3,3'-dimethyldiphenylmethane / o-dianisidine diisocyanate, 4,4'-diamino- Three
3'-Dimethyldiphenylmethane / methylenebis (4-
Isocyanato-2-methylbenzene), 4,4'-diamino-3,3'-dimethyldiphenylmethane / 4,
4'-diphenylmethane diisocyanate (MDI),
4,4'-diamino-3,3'-dimethyldiphenylmethane / 2,4-toluene diisocyanate (2,4-T
DI), 4,4'-diamino-3,3'-dimethyldiphenylmethane / 2,6-toluene diisocyanate (2,6-TDI), 4,4'-diamino-3,3'-
Dimethyldiphenylmethane / bis (4-isocyanatophenyl) ether, 4,4'-diamino-3,3'-
Dimethyldiphenylmethane / p-phenylene diisocyanate, 4,4′-diamino-3,3′-dimethyldiphenylmethane / 1,5-naphthalene diisocyanate,
3,3'-dimethoxy-4,4'-diaminobiphenyl / 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diaminobiphenyl / o-dia Nisidine diisocyanate, 3,
3'-dimethoxy-4,4'-diaminobiphenyl / methylenebis (4-isocyanato-2-methylbenzene), 3,3'-dimethoxy-4,4'-diaminobiphenyl / 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethoxy-4,4'-diaminobiphenyl / 2,4-toluene diisocyanate (2,4-TDI), 3,3'-dimethoxy-4,4 '
-Diaminobiphenyl / 2,6-toluene diisocyanate (2,6-TDI), 3,3'-dimethoxy-4,
4'-diaminobiphenyl / bis (4-isocyanatophenyl) ether, 3,3'-dimethoxy-4,4 '
-Diaminobiphenyl / p-phenylene diisocyanate, 3,3'-dimethoxy-4,4'-diaminobiphenyl / 1,5-naphthalene diisocyanate, 3,3 '
-Dimethyl-4,4'-diaminobiphenyl / 3,3 '
-Dimethyldiphenyl-4,4'-diisocyanate,
3,3'-dimethyl-4,4'-diaminobiphenyl /
o-dianisidine diisocyanate, 3,3'-dimethyl-4,4'-diaminobiphenyl / methylenebis (4
-Isocyanato-2-methylbenzene), 3,3'-
Dimethyl-4,4'-diaminobiphenyl / 4,4'-
Diphenylmethane diisocyanate (MDI), 3,
3'-dimethyl-4,4'-diaminobiphenyl / 2,
4-toluene diisocyanate (2,4-TDI),
3,3'-dimethyl-4,4'-diaminobiphenyl /
2,6-Toluene diisocyanate (2,6-TD
I), 3,3'-dimethyl-4,4'-diaminobiphenyl / bis (4-isocyanatophenyl) ether,
3,3'-dimethyl-4,4'-diaminobiphenyl /
p-Phenylene diisocyanate, 3,3′-dimethyl-4,4′-diaminobiphenyl / 1,5-naphthalene diisocyanate, 4,4′-methylene-bis (2-chloroaniline) / 3,3 ′ -Dimethyldiphenyl-4,
4'-diisocyanate, 4,4'-methylene-bis (2-chloroaniline) / o-dianisidine diisocyanate, 4,4'-methylene-bis (2-chloroaniline) / methylenebis (4-isocyanate) Nato-2-methylbenzene), 4,4'-methylene-bis (2-chloroaniline) / 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-methylene-bis (2-chloroaniline) / 2,4-toluene diisocyanate (2,
4-TDI), 4,4'-methylene-bis (2-chloroaniline) / 2,6-toluene diisocyanate (2,
6-TDI), 4,4'-methylene-bis (2-chloroaniline) / bis (4-isocyanatophenyl) ether, 4,4'-methylene-bis (2-chloroaniline) / p-phenylenediene Isocyanate, 4,4'-methylene-bis (2-chloroaniline) / 1,5-naphthalene diisocyanate, 1,3-diamino-5-cyanobenzene / 2,6-naphthalene diisocyanate, The method for producing a polyurea film according to (1), (2), (3) or (4).

[0029]

【Example】

Example 1 First, the vapor deposition polymerization chamber 1 with the valves 4, 5 and 8 closed.
A glass substrate 11 having a length of 75 mm, a width of 26 mm, and a thickness of 1 mm is held in a substrate holder 12 inside, and one of evaporation sources 13 and 13 in the vapor deposition polymerization chamber 1 has 4,4 'as a raw material monomer (a). -Diaminodiphenylmethane (hereinafter referred to as raw material monomer a ₁ ) and the other, as raw material monomer (b), 4,4′-methylenediphenyl diisocyanate (hereinafter referred to as raw material monomer b ₁ ) respectively,
With the shutter 16 closed, the valves 4, 5 and 8 are opened so that the total pressure in the vapor deposition polymerization chamber 1, the exposure chamber 2 and the developing chamber 3 is reduced to the vacuum exhaust system 6 of the vacuum chamber 7 and the vacuum exhaust system of the vacuum chamber 10. 1.3 × 10 ⁻³ Pa (1 × 10 ⁻⁵ Tor
After setting to r), each valve 4, 5, 8 was closed.

Next, while measuring the amount of evaporation of each raw material monomer a ₁ and b ₁ from the evaporation sources 13 and 13 with the evaporation monitors 14 and 14, the raw material monomer a is heated by the heaters 15 and 15.
₁ was heated to 110 ± 1.0 ° C., and the raw material monomer b ₁ was heated to 70 ± 0.2 ° C., respectively.

Then, after the raw material monomers a ₁ and b ₁ reach a predetermined temperature to obtain a required evaporation amount, the shutter 16 is opened and the surface of the substrate 11 held by the substrate holder 12 in the vapor deposition polymerization chamber 1 is exposed. After depositing the raw material monomers a ₁ and b ₁ at a deposition rate of 200 Å / min to a film thickness of 2500 Å and depositing them,
The shutter 16 was closed, and a polyurea polymerization reaction was caused on the surface of the substrate 11 to form a polyurea film.

The raw material monomers a ₁ and b ₁ were evaporated at a molar ratio of 1: 1 by adjusting the evaporation amount so that a polyurea film was stoichiometrically formed. The pressure in the vapor deposition polymerization chamber 1 during evaporation of the raw material monomers a ₁ and b ₁ was 6.5 × 10 ⁻³ Pa (5 × 10 ⁻⁵ Torr).

Next, only the valve 4 between the vapor deposition polymerization chamber 1 and the exposure chamber 2 is opened, and the pressure of the substrate 11 on which the polyurea film is formed in the vapor deposition polymerization chamber 1 is 1.3 × 10 ^{−3 in} advance. Pa (1
After being transferred into the exposure chamber 2 set to × 10 ⁻⁵ Torr), the valve 4 is closed and ten photomasks made of stainless steel having a width of 5 mm and a length of 5 mm and having a rectangular shape are punched. The polyurea film side of the surface of the substrate 11 was fixed on 19. Subsequently, the polyurea film was irradiated with ultraviolet rays having a central wavelength of 254 nm and 10 W from the ultraviolet ray source 18 through the photomask 19 for 5 minutes.

Next, only the valve 4 between the exposure chamber 2 and the developing chamber 3 is opened, and the substrate 11 on which the polyurea film has been irradiated with ultraviolet rays in the exposure chamber 2 has a pressure of 1.3 × 10 ^{−3 in} advance. Pa (1
After being transported into the developing chamber 3 set to × 10 ⁻⁵ Torr), the valve 4 is closed and the substrate 11 is heated by the heater 2.
It was fixed in place below zero. Subsequently, the heater 11 was used to develop the substrate 11 by heat treatment at a temperature of 300 ° C. for 5 minutes.

Next, only the valve 8 between the developing chamber 3 and the vacuum chamber 10 is opened, and the substrate 11 on which the polyurea film has been subjected to the developing treatment in the developing chamber 3 has a pressure of 1.3 × 10 ^{−. 3} Pa
After being transferred into the vacuum chamber 10 set to (1 × 10 ⁻⁵ Torr), the valve 8 was closed and the inside of the vacuum chamber 10 was brought to atmospheric pressure, and then the substrate 11 was taken out from the vacuum chamber 10.

When the polyurea film on the surface of the substrate 11 taken out from the vacuum chamber 10 was examined, the polyurea film on the irradiated portion irradiated with the ultraviolet rays remained on the substrate surface with a film thickness of 1800Å.
It was found that the polyurea film in the portion not irradiated with ultraviolet rays was depolymerized and did not remain on the substrate surface, and a pattern having the same shape as the pattern shape of the photomask was formed.

Example 2 As one raw material monomer (a), 4,4'-diaminodiphenyl ether (hereinafter referred to as raw material monomer a ₂ ) was used.
And the heating temperature was set to 135 ± 2 ° C., and methylenediphenyl 4,4′-diisocyanate (hereinafter referred to as the raw material monomer b ₂ ) was used as the other raw material monomer (b), and the heating temperature was 70 ± 0. A polyurea film was formed on the surface of the substrate 11 in the same manner as in Example 1 except that the temperature was 2 ° C.

Then, the polyurea film formed on the surface of the substrate 11 was irradiated with ultraviolet rays in the same manner as in Example 1, and after developing with a heating device, the polyurea film was examined. Similarly, it was found that the polyurea film in the unirradiated portion which was not irradiated with ultraviolet rays was removed by depolymerization and did not remain on the substrate surface, and a pattern having the same shape as the pattern shape of the photomask was formed.

Example 3 As one raw material monomer (a), 4,4'-diaminodiphenylmethane (hereinafter referred to as raw material monomer a ₃ ) was used, the heating temperature was 100 ± 0.2 ° C., and the other raw material monomer was used. As (b), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (hereinafter referred to as raw material monomer b
₃ ) was used and the heating temperature was set to 135 ± 1 ° C. to form a polyurea film on the surface of the substrate 11 in the same manner as in Example 1.

Then, the polyurea film formed on the surface of the substrate 11 was irradiated with ultraviolet rays in the same manner as in Example 1 and developed by a heating device, and then the polyurea film was examined. Similarly, it was found that the polyurea film in the unirradiated portion which was not irradiated with ultraviolet rays was removed by depolymerization and did not remain on the substrate surface, and a pattern having the same shape as the pattern shape of the photomask was formed.

The polyurea film was formed on the surface of the substrate in the same manner as in Example 1 except that the development of the polyurea film, that is, the heating temperature of the substrate by the heating device was 290 ° C. and the heating time was 10 minutes. And the polyurea film was irradiated with ultraviolet rays.

After the development, the polyurea film was examined. As in Example 1, the unexposed portion of the polyurea film which had not been irradiated with ultraviolet rays was removed by depolymerization and was not left on the substrate surface. It was found that a pattern having the same shape as the pattern shape of the photomask was formed.

Example 5 A polyurea film was formed on the surface of a substrate by the same method as in Example 1 except that the development on the polyurea film, that is, the heating temperature of the substrate by the heating device was 310 ° C. Ultraviolet irradiation was performed on the polyurea film.

After the development, the polyurea film was examined. As in Example 1, the unexposed portion of the polyurea film which had not been irradiated with ultraviolet rays was removed by depolymerization and did not remain on the substrate surface. It was found that a pattern having the same shape as the pattern shape of the photomask was formed.

Example 6 Instead of a ₁ in Example 1, 3,3'-dimethyl-4,
Example 1 except that 4'-diaminobiphenyl is used
The same vapor deposition polymerization, ultraviolet irradiation, and development were performed. As a result, the polyurea film irradiated with ultraviolet rays remains on the substrate surface as it is, and the polyurea film unirradiated with ultraviolet rays depolymerizes and does not remain on the substrate surface. It was found that the same pattern was formed.

Example 7 As one raw material monomer (a), 3,3'-dimethyl-4,4'-diaminophenyl was used, the heating temperature was 110 ± 1 ° C., and the other raw material monomer (b) was used. A polyurea film was formed on the surface of the substrate 11 in the same manner as in Example 1 except that 3,3′-dimethyldiphenyl-4,4′-diisocyanate was used and the heating temperature was 135 ± 1 ° C. did.

Then, the polyurea film formed on the surface of the substrate 11 was irradiated with ultraviolet rays in the same manner as in Example 1, and after developing with a heating device, the polyurea film was examined. Similarly, it was found that the polyurea film in the unirradiated portion which was not irradiated with ultraviolet rays was removed by depolymerization and did not remain on the substrate surface, and a pattern having the same shape as the pattern shape of the photomask was formed.

Example 8 4,4'-diaminodiphenyl ether was used as one raw material monomer (a), and the heating temperature was 135 ± 1.
C., 1,3-bis (isocyanatomethyl) benzene was used as the other raw material monomer (b), the heating temperature was 42. +-. 0.2.degree. C., and the temperature of the substrate 11 was 10.degree.
Example 1 except that the temperature in the vapor deposition polymerization chamber 1 during evaporation of the raw material monomers (a) and (b) was 1.8 × 10 ⁻⁴ Torr and the rate was 17 Å / min. A polyurea film was formed on the surface of the substrate 11 by the same method. Then, the polyurea film formed on the surface of the substrate 11 was irradiated with ultraviolet rays in the same manner as in Example 1 above, and was developed with a heating device, and then the polyurea film was examined. It was found that the polyurea film in the unirradiated unexposed area was removed by depolymerization and did not remain on the substrate surface, and a pattern having the same shape as the pattern shape of the photomask was formed.

Example 9 As one raw material monomer (a), 1,3-diamino-
Using 5-cyanobenzene, the heating temperature is 104 ± 1
C. and 2,6-naphthalene diisocyanate as the other raw material monomer (b), and the evaporation temperature is 75
The temperature in the substrate 11 was kept at 5 ° C., and the pressure in the vapor deposition polymerization chamber 1 at the time of evaporation of the raw material monomers (a) and (b) was set to 4.0 × 10 ⁻⁵ Torr. A polyurea film was formed on the surface of the substrate 11 by the same method as in Example 1 except for the above. Then, the polyurea film formed on the surface of the substrate 11 is irradiated with ultraviolet rays in the same manner as in Example 1,
After development with a heating device, the polyurea film was examined. As in the case of Example 1, the unexposed portion of the polyurea film that had not been irradiated with ultraviolet rays was removed by depolymerization and did not remain on the substrate surface. It was found that a pattern having the same shape as the pattern shape of the photomask was formed.

In each of the above embodiments, the substrate 11 was held in the substrate holder 12 in the vapor deposition polymerization chamber 1, but the vacuum chamber 7 was used.
You can do it inside.

In the apparatus shown in FIG. 1, the evacuation chamber 6, the exposure chamber 2, and the developing chamber 3 are evacuated to a vacuum evacuation system 6 of a vacuum chamber 7.
The vacuum chamber 10 is evacuated by either one or both of the vacuum exhaust systems 9. However, a vacuum pump or other vacuum exhaust system is installed in each of the vapor deposition polymerization chamber 1, the exposure chamber 2, and the developing chamber 3, and each chamber You may make it exhaust every time.

In the present invention, the step of forming a polyurea film on the surface of a substrate in a vacuum, the step of exposing the polyurea film by ultraviolet irradiation, and the step of developing by depolymerizing the polyurea of the unexposed portion after ultraviolet irradiation are consecutively performed. Therefore, it is possible to consistently form a pattern on the synthetic resin film on the substrate surface in a vacuum by connecting with other vacuum processes such as an electrode deposition process and an insulating film formation process.

[0053]

[Effect] According to the present invention, a vapor deposition polymerization polyurea film which does not cause thermal decomposition even when heated to 230 to 300 ° C. can be obtained. The combination of the method of the present invention and the characteristics of the vapor deposition polymerization polyurea film provides an advantageous pattern forming method.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of one embodiment of a pattern forming apparatus of the present invention.

[Explanation of symbols]

 1 vapor deposition polymerization chamber 2 exposure chamber 3 developing chamber 4 valve 5 valve 6 vacuum exhaust system 7 vacuum chamber 8 valve 9 vacuum exhaust system 10 vacuum chamber 11 substrate 12 substrate holder 13 evaporation source 14 evaporation monitor 15 heater 16 shutter 17 partition plate 18 ultraviolet light Source 19 Photomask 20 Heating device a Raw material monomer b Raw material monomer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayuki Iijima 5-9-7 Tokodai, Tsukuba, Ibaraki Nihon Sky Technology Co., Ltd. Tsukuba Institute for Supermaterials

Claims (3)

[Claims] 1. A (a) diamine component and a (b) diisocyanate component are evaporated from different evaporation sources in a vacuum, and a polyurea film is formed on the surface of a substrate by vapor deposition polymerization.
Next, a method for producing a polyurea film, which comprises irradiating the polyurea film with an ultraviolet ray and / or an electron beam. 2. A (a) diamine component, (b) diisocyanate component and (c) sensitizer are evaporated from different evaporation sources in a vacuum, and a polyurea film is formed on the surface of the substrate by vapor deposition polymerization. A method for producing a polyurea film, which comprises forming the polyurea film and then irradiating the polyurea film with ultraviolet rays and / or electron beams. 3. A (a) diamine component and a (b) diisocyanate component are evaporated from different evaporation sources in a vacuum, and a polyurea film is formed on the surface of the substrate by vapor deposition polymerization.
Next, (c) a sensitizer is vapor-deposited from another evaporation source on the polyurea film, which is repeated if necessary, and then ultraviolet rays and / or electron beams are irradiated onto the polyurea film. Urea film manufacturing method.